Chapter 6 The Structure of Atoms

Properties of Waves

A waveA periodic oscillation that transmits energy through space. is a periodic oscillation that transmits energy through space. Anyone who has visited a beach or dropped a stone into a puddle has observed waves traveling through water (Figure 6.1 "A Wave in Water"). These waves are produced when wind, a stone, or some other disturbance, such as a passing boat, transfers energy to the water, causing the surface to oscillate up and down as the energy travels outward from its point of origin. As a wave passes a particular point on the surface of the water, anything floating there moves up and down.

Figure 6.2 Important Properties of Waves

(a) Wavelength (λ), frequency (ν, labeled in Hz), and amplitude are indicated on this drawing of a wave. (b) The wave with the shortest wavelength has the greatest number of wavelengths per unit time (i.e., the highest frequency). If two waves have the same frequency and speed, the one with the greater amplitude has the higher energy.

Waves have characteristic properties (Figure 6.2 "Important Properties of Waves"). As you may have noticed in Figure 6.1 "A Wave in Water", waves are periodicPhenomena, such as waves, that repeat regularly in both space and time.; that is, they repeat regularly in both space and time. The distance between two corresponding points in a wave—between the midpoints of two peaks, for example, or two troughs—is the wavelength (λ)The distance between two corresponding points in a wave—between the midpoints of two peaks or two troughs..λ is the lowercase Greek lambda, and ν is the lowercase Greek nu. Wavelengths are described by a unit of distance, typically meters. The frequency (ν)The number of oscillations (i.e., of a wave) that pass a particular point in a given period of time. of a wave is the number of oscillations that pass a particular point in a given period of time. The usual units are oscillations per second (1/s = s⁻¹), which in the SI system is called the hertz (Hz).Named after German physicist Heinrich Hertz (1857–1894), a pioneer in the field of electromagnetic radiation. The amplitudeThe vertical height of a wave, which is defined as half the peak-to-trough height., or vertical height, of a wave is defined as half the peak-to-trough height; as the amplitude of a wave with a given frequency increases, so does its energy. As you can see in Figure 6.2 "Important Properties of Waves", two waves can have the same amplitude but different wavelengths and vice versa. The distance traveled by a wave per unit time is its speed (v)The distance traveled by a wave per unit time., which is typically measured in meters per second (m/s). The speed of a wave is equal to the product of its wavelength and frequency:

Water waves are slow compared to sound waves, which can travel through solids, liquids, and gases. Whereas water waves may travel a few meters per second, the speed of sound in dry air at 20°C is 343.5 m/s. Ultrasonic waves, which travel at an even higher speed (>1500 m/s) and have a greater frequency, are used in such diverse applications as locating underwater objects and the medical imaging of internal organs.

Electromagnetic Radiation

Water waves transmit energy through space by the periodic oscillation of matter (the water). In contrast, energy that is transmitted, or radiated, through space in the form of periodic oscillations of electric and magnetic fields is known as electromagnetic radiationEnergy that is transmitted, or radiated, through space in the form of periodic oscillations of electric and magnetic fields. (Figure 6.3 "The Nature of Electromagnetic Radiation"). Some forms of electromagnetic radiation are shown in Figure 6.4 "The Electromagnetic Spectrum". In a vacuum, all forms of electromagnetic radiation—whether microwaves, visible light, or gamma rays—travel at the speed of light (c)The speed with which all forms of electromagnetic radiation travel in a vacuum., a fundamental physical constant with a value of 2.99792458 × 10⁸ m/s (which is about 3.00 ×10⁸ m/s or 1.86 × 10⁵ mi/s). This is about a million times faster than the speed of sound.

Figure 6.3 The Nature of Electromagnetic Radiation

All forms of electromagnetic radiation consist of perpendicular oscillating electric and magnetic fields.

Because the various kinds of electromagnetic radiation all have the same speed (c), they differ in only wavelength and frequency. As shown in Figure 6.4 "The Electromagnetic Spectrum" and Table 6.1 "Common Wavelength Units for Electromagnetic Radiation", the wavelengths of familiar electromagnetic radiation range from 10¹ m for radio waves to 10⁻¹² m for gamma rays, which are emitted by nuclear reactions. By replacing v with c in Equation 6.1, we can show that the frequency of electromagnetic radiation is inversely proportional to its wavelength:

For example, the frequency of radio waves is about 10⁸ Hz, whereas the frequency of gamma rays is about 10²⁰ Hz. Visible light, which is electromagnetic radiation that can be detected by the human eye, has wavelengths between about 7 × 10⁻⁷ m (700 nm, or 4.3 × 10¹⁴ Hz) and 4 × 10⁻⁷ m (400 nm, or 7.5 × 10¹⁴ Hz). Within this range, the eye perceives radiation of different wavelengths (or frequencies) as light of different colors, ranging from red to violet in order of decreasing wavelength. The components of white light—a mixture of all the frequencies of visible light—can be separated by a prism, as shown in part (b) in Figure 6.4 "The Electromagnetic Spectrum". A similar phenomenon creates a rainbow, where water droplets suspended in the air act as tiny prisms.

Figure 6.4 The Electromagnetic Spectrum

(a) This diagram shows the wavelength and frequency ranges of electromagnetic radiation. The visible portion of the electromagnetic spectrum is the narrow region with wavelengths between about 400 and 700 nm. (b) When white light is passed through a prism, it is split into light of different wavelengths, whose colors correspond to the visible spectrum.

As you will soon see, the energy of electromagnetic radiation is directly proportional to its frequency and inversely proportional to its wavelength:

Whereas visible light is essentially harmless to our skin, ultraviolet light, with wavelengths of ≤ 400 nm, has enough energy to cause severe damage to our skin in the form of sunburn. Because the ozone layer described in Chapter 3 "Chemical Reactions" absorbs sunlight with wavelengths less than 350 nm, it protects us from the damaging effects of highly energetic ultraviolet radiation.

In Section 6.2 "The Quantization of Energy" and Section 6.3 "Atomic Spectra and Models of the Atom", we describe how scientists developed our current understanding of the structure of atoms using the scientific method described in Chapter 1 "Introduction to Chemistry". You will discover why scientists had to rethink their classical understanding of the nature of electromagnetic energy, which clearly distinguished between the particulate behavior of matter and the wavelike nature of energy.

Blackbody Radiation

One phenomenon that seemed to contradict the theories of classical physics was blackbody radiationElectromagnetic radiation whose wavelength and color depends on the temperature of the object., the energy emitted by an object when it is heated. The wavelength of energy emitted by an object depends on only its temperature, not its surface or composition. Hence an electric stove burner or the filament of a space heater glows dull red or orange when heated, whereas the much hotter tungsten wire in an incandescent light bulb gives off a yellowish light (Figure 6.5 "Blackbody Radiation").

Figure 6.5 Blackbody Radiation

When heated, all objects emit electromagnetic radiation whose wavelength (and color) depends on the temperature of the object. A relatively low-temperature object, such as an electric stove element, on a low setting appears red, whereas a higher-temperature object, such as the filament of an incandescent light bulb, appears yellow or white.

The intensity of radiation is a measure of the energy emitted per unit area. A plot of the intensity of blackbody radiation as a function of wavelength for an object at various temperatures is shown in Figure 6.6 "Relationship between the Temperature of an Object and the Spectrum of Blackbody Radiation It Emits". One of the major assumptions of classical physics was that energy increased or decreased in a smooth, continuous manner. For example, classical physics predicted that as wavelength decreased, the intensity of the radiation an object emits should increase in a smooth curve without limit at all temperatures, as shown by the broken line for 6000 K in Figure 6.6 "Relationship between the Temperature of an Object and the Spectrum of Blackbody Radiation It Emits". Thus classical physics could not explain the sharp decrease in the intensity of radiation emitted at shorter wavelengths (primarily in the ultraviolet region of the spectrum), which we now refer to as the “ultraviolet catastrophe.” In 1900, however, the German physicist Max Planck (1858–1947) explained the ultraviolet catastrophe by proposing that the energy of electromagnetic waves is quantized rather than continuous. This means that for each temperature, there is a maximum intensity of radiation that is emitted in a blackbody object, corresponding to the peaks in Figure 6.6 "Relationship between the Temperature of an Object and the Spectrum of Blackbody Radiation It Emits", so the intensity does not follow a smooth curve as the temperature increases, as predicted by classical physics. Thus energy could be gained or lost only in integral multiples of some smallest unit of energy, a quantumThe smallest possible unit of energy. Energy can be gained or lost only in integral multiples of a quantum..

Figure 6.6 Relationship between the Temperature of an Object and the Spectrum of Blackbody Radiation It Emits

At relatively low temperatures, most radiation is emitted at wavelengths longer than 700 nm, which is in the infrared portion of the spectrum. The dull red glow of the electric stove element in Figure 6.5 "Blackbody Radiation" is due to the small amount of radiation emitted at wavelengths less than 700 nm, which the eye can detect. As the temperature of the object increases, the maximum intensity shifts to shorter wavelengths, successively resulting in orange, yellow, and finally white light. At high temperatures, all wavelengths of visible light are emitted with approximately equal intensities. The white light spectrum shown for an object at 6000 K closely approximates the spectrum of light emitted by the sun (Figure 6.14 "The Visible Spectrum of Sunlight"). Note the sharp decrease in the intensity of radiation emitted at wavelengths below 400 nm, which constituted the ultraviolet catastrophe. The classical prediction fails to fit the experimental curves entirely and does not have a maximum intensity.

Although quantization may seem to be an unfamiliar concept, we encounter it frequently. For example, US money is integral multiples of pennies. Similarly, musical instruments like a piano or a trumpet can produce only certain musical notes, such as C or F sharp. Because these instruments cannot produce a continuous range of frequencies, their frequencies are quantized. Even electrical charge is quantized: an ion may have a charge of −1 or −2 but not −1.33.

Planck postulated that the energy of a particular quantum of radiant energy could be described explicitly by the equation

where the proportionality constant h is called Planck’s constant, one of the most accurately known fundamental constants in science. For our purposes, its value to four significant figures is generally sufficient:

As the frequency of electromagnetic radiation increases, the magnitude of the associated quantum of radiant energy increases. By assuming that energy can be emitted by an object only in integral multiples of hν, Planck devised an equation that fit the experimental data shown in Figure 6.6 "Relationship between the Temperature of an Object and the Spectrum of Blackbody Radiation It Emits". We can understand Planck’s explanation of the ultraviolet catastrophe qualitatively as follows: At low temperatures, radiation with only relatively low frequencies is emitted, corresponding to low-energy quanta. As the temperature of an object increases, there is an increased probability of emitting radiation with higher frequencies, corresponding to higher-energy quanta. At any temperature, however, it is simply more probable for an object to lose energy by emitting n lower-energy quanta than a single very high-energy quantum that corresponds to ultraviolet radiation. The result is a maximum in the plot of intensity of emitted radiation versus wavelength, as shown in Figure 6.6 "Relationship between the Temperature of an Object and the Spectrum of Blackbody Radiation It Emits", and a shift in the position of the maximum to lower wavelength (higher frequency) with increasing temperature.

At the time he proposed his radical hypothesis, Planck could not explain why energies should be quantized. Initially, his hypothesis explained only one set of experimental data—blackbody radiation. If quantization were observed for a large number of different phenomena, then quantization would become a law (as defined in Chapter 1 "Introduction to Chemistry"). In time, a theory might be developed to explain that law. As things turned out, Planck’s hypothesis was the seed from which modern physics grew.

The Photoelectric Effect

Only five years after he proposed it, Planck’s quantization hypothesis was used to explain a second phenomenon that conflicted with the accepted laws of classical physics. When certain metals are exposed to light, electrons are ejected from their surface (Figure 6.7 "The Photoelectric Effect"). Classical physics predicted that the number of electrons emitted and their kinetic energy should depend on only the intensity of the light, not its frequency. In fact, however, each metal was found to have a characteristic threshold frequency of light; below that frequency, no electrons are emitted regardless of the light’s intensity. Above the threshold frequency, the number of electrons emitted was found to be proportional to the intensity of the light, and their kinetic energy was proportional to the frequency. This phenomenon was called the photoelectric effectA phenomenon in which electrons are ejected from the surface of a metal that has been exposed to light..

Figure 6.7 The Photoelectric Effect

(a) Irradiating a metal surface with photons of sufficiently high energy causes electrons to be ejected from the metal. (b) A photocell that uses the photoelectric effect, similar to those found in automatic door openers. When light strikes the metal cathode, electrons are emitted and attracted to the anode, resulting in a flow of electrical current. If the incoming light is interrupted by, for example, a passing person, the current drops to zero. (c) In contrast to predictions using classical physics, no electrons are emitted when photons of light with energy less than E_o, such as red light, strike the cathode. The energy of violet light is above the threshold frequency, so the number of emitted photons is proportional to the light’s intensity.

Albert Einstein (1879–1955; Nobel Prize in Physics, 1921) quickly realized that Planck’s hypothesis about the quantization of radiant energy could also explain the photoelectric effect. The key feature of Einstein’s hypothesis was the assumption that radiant energy arrives at the metal surface in particles that we now call photonsA quantum of radiant energy, each of which possesses a particular energy $E$ given by $E=h\nu .$, each possessing a particular energy E given by Equation 6.5. Einstein postulated that each metal has a particular electrostatic attraction for its electrons that must be overcome before an electron can be emitted from its surface (E_o = hν_o). If photons of light with energy less than E_o strike a metal surface, no single photon has enough energy to eject an electron, so no electrons are emitted regardless of the intensity of the light. If a photon with energy greater than E_o strikes the metal, then part of its energy is used to overcome the forces that hold the electron to the metal surface, and the excess energy appears as the kinetic energy of the ejected electron:

When a metal is struck by light with energy above the threshold energy E_o, the number of emitted electrons is proportional to the intensity of the light beam, which corresponds to the number of photons per square centimeter, but the kinetic energy of the emitted electrons is proportional to the frequency of the light. Thus Einstein showed that the energy of the emitted electrons depended on the frequency of the light, contrary to the prediction of classical physics.

Planck’s and Einstein’s postulate that energy is quantized is in many ways similar to Dalton’s description of atoms. Both theories are based on the existence of simple building blocks, atoms in one case and quanta of energy in the other. The work of Planck and Einstein thus suggested a connection between the quantized nature of energy and the properties of individual atoms. In fact, Einstein’s Nobel Prize was awarded for his work on the photoelectric effect (not for his more famous equation E = mc²), demonstrating its fundamental importance.

Recently, scientists have theorized that even our sense of smell has its basis in quantum physics. Preliminary research indicates that odorant molecules absorb a quantum of energy that causes their bonds to vibrate at a specific frequency. Because different assemblages of molecules have different characteristic frequencies, these vibrations seem to act as a molecular signature that can be detected as an odor. Studies with flies show that they can distinguish between similar molecules with different vibrational frequencies. This vibrational theory of smell could serve as a discriminatory process in nature in other ways and is an active area of research.

Example 2

Figure 6.8 A Beam of Red Light Emitted by a Ruby Laser

Ruby lasers, which emit red light at a wavelength of 694.3 nm, are used to read bar codes. When used for commercial applications, such lasers are generally designed to emit radiation over a narrow range of wavelengths to reduce their cost.

A ruby laser, a device that produces light in a narrow range of wavelengths (Section 6.3 "Atomic Spectra and Models of the Atom"), emits red light at a wavelength of 694.3 nm (Figure 6.8 "A Beam of Red Light Emitted by a Ruby Laser"). What is the energy in joules of a

1. single photon?
2. mole of photons?

Given: wavelength

Asked for: energy of single photon and mole of photons

Strategy:

A Use Equation 6.2 and Equation 6.5 to calculate the energy in joules.

B Multiply the energy of a single photon by Avogadro’s number to obtain the energy in a mole of photons.

Solution:

The energy of a single photon is given by E = hν = hc/λ.

$$E=\frac{(6.626\times {10}^{-34}\text{ J•}\cancel{\text{s}}\text{)(2}\text{.998}\times {\text{10}}^8\cancel{\text{m}}\text{•}\cancel{{\text{s}}^{-1}})}{694.3\times {10}^{-9}\cancel{\text{m}}}=2.861\times {10}^{-19}\text{ J}$$

B To calculate the energy in a mole of photons, we multiply the energy of a single photon by the number of photons in a mole (Avogadro’s number). If we write the energy of a photon as 2.861 × 10⁻¹⁹ J/photon, we obtain the energy of a mole of photons with wavelength 694.3 nm:

$$\begin{array}{ll}E\hfill & =\left(\frac{2.861\times {10}^{-19}\text{ J}}{\cancel{\text{photon}}}\right)\left(\frac{6.022\times {10}^{23}\cancel{\text{photon}}}{\text{mol}}\right)\hfill \\ \hfill & =1.723\times {10}^5\text{ J/mol}\hfill \\ \hfill & =172.3\text{ kJ/mol}\hfill \end{array}$$

This energy is of the same magnitude as some of the enthalpies of reaction in Chapter 5 "Energy Changes in Chemical Reactions", and, as you will see in Chapter 8 "Ionic versus Covalent Bonding", it is comparable to the strength of many chemical bonds. As a result, light can be used to initiate chemical reactions. In fact, an entire area of chemistry called photochemistry is devoted to studying such processes. In the phenomenon of photosynthesis, green plants use the energy of visible light to convert carbon dioxide and water into sugars such as glucose.

Exercise

An x-ray generator, such as those used in hospitals, emits radiation with a wavelength of 1.544 Å.

1. What is the energy in joules of a single photon?
2. What is the energy in joules of a mole of photons?
3. How many times more energetic is a single x-ray photon of this wavelength than a photon emitted by a ruby laser?

Answer:

1. 1.287 × 10⁻¹⁵ J/photon
2. 7.748 × 10⁸ J/mol = 7.748 × 10⁵ kJ/mol
3. 4497 times

Line Spectra

Although objects at high temperature emit a continuous spectrum of electromagnetic radiation (Figure 6.6 "Relationship between the Temperature of an Object and the Spectrum of Blackbody Radiation It Emits"), a different kind of spectrum is observed when pure samples of individual elements are heated. For example, when a high-voltage electrical discharge is passed through a sample of hydrogen gas at low pressure, the resulting individual isolated hydrogen atoms caused by the dissociation of H₂ emit a red light. Unlike blackbody radiation, the color of the light emitted by the hydrogen atoms does not depend greatly on the temperature of the gas in the tube. When the emitted light is passed through a prism, only a few narrow lines, called a line spectrumA spectrum in which light of only a certain wavelength is emitted or absorbed, rather than a continuous range of wavelengths., are seen (Figure 6.9 "The Emission of Light by Hydrogen Atoms"), rather than a continuous range of colors. The light emitted by hydrogen atoms is red because, of its four characteristic lines, the most intense line in its spectrum is in the red portion of the visible spectrum, at 656 nm. With sodium, however, we observe a yellow color because the most intense lines in its spectrum are in the yellow portion of the spectrum, at about 589 nm.

Figure 6.9 The Emission of Light by Hydrogen Atoms

(a) A sample of excited hydrogen atoms emits a characteristic red light. (b) When the light emitted by a sample of excited hydrogen atoms is split into its component wavelengths by a prism, four characteristic violet, blue, green, and red emission lines can be observed, the most intense of which is at 656 nm.

Such emission spectra were observed for many other elements in the late 19th century, which presented a major challenge because classical physics was unable to explain them. Part of the explanation is provided by Planck’s equation (Equation 6.5): the observation of only a few values of λ (or ν) in the line spectrum meant that only a few values of E were possible. Thus the energy levels of a hydrogen atom had to be quantized; in other words, only states that had certain values of energy were possible, or allowed. If a hydrogen atom could have any value of energy, then a continuous spectrum would have been observed, similar to blackbody radiation.

In 1885, a Swiss mathematics teacher, Johann Balmer (1825–1898), showed that the frequencies of the lines observed in the visible region of the spectrum of hydrogen fit a simple equation that can be expressed as follows:

where n = 3, 4, 5, 6. As a result, these lines are known as the Balmer series. The Swedish physicist Johannes Rydberg (1854–1919) subsequently restated and expanded Balmer’s result in the Rydberg equation:

where n₁ and n₂ are positive integers, n₂ > n₁, and $ℛ\text{,}$ the Rydberg constant, has a value of 1.09737 × 10⁷ m⁻¹.

Like Balmer’s equation, Rydberg’s simple equation described the wavelengths of the visible lines in the emission spectrum of hydrogen (with n₁ = 2, n₂ = 3, 4, 5,…). More important, Rydberg’s equation also described the wavelengths of other series of lines that would be observed in the emission spectrum of hydrogen: one in the ultraviolet (n₁ = 1, n₂ = 2, 3, 4,…) and one in the infrared (n₁ = 3, n₂ = 4, 5, 6). Unfortunately, scientists had not yet developed any theoretical justification for an equation of this form.

The Bohr Model

In 1913, a Danish physicist, Niels Bohr (1885–1962; Nobel Prize in Physics, 1922), proposed a theoretical model for the hydrogen atom that explained its emission spectrum. Bohr’s model required only one assumption: The electron moves around the nucleus in circular orbits that can have only certain allowed radii. As discussed in Chapter 1 "Introduction to Chemistry", Rutherford’s earlier model of the atom had also assumed that electrons moved in circular orbits around the nucleus and that the atom was held together by the electrostatic attraction between the positively charged nucleus and the negatively charged electron. Although we now know that the assumption of circular orbits was incorrect, Bohr’s insight was to propose that the electron could occupy only certain regions of space.

Using classical physics, Bohr showed that the energy of an electron in a particular orbit is given by

where $ℛ$ is the Rydberg constant, h is Planck’s constant, c is the speed of light, and n is a positive integer corresponding to the number assigned to the orbit, with n = 1 corresponding to the orbit closest to the nucleus.The negative sign in Equation 6.9 is a convention indicating that the electron-nucleus pair has a lower energy when they are near each other than when they are infinitely far apart, corresponding to n = ∞. The latter condition is arbitrarily assigned an energy of zero. Thus the orbit with n = 1 is the lowest in energy. Because a hydrogen atom with its one electron in this orbit has the lowest possible energy, this is the ground stateThe most stable arrangement of electrons for an element or a compound., the most stable arrangement for a hydrogen atom. As n increases, the radius of the orbit increases; the electron is farther from the proton, which results in a less stable arrangement with higher potential energy (Figure 6.10 "The Bohr Model of the Hydrogen Atom"). A hydrogen atom with an electron in an orbit with n > 1 is therefore in an excited stateAny arrangement of electrons that is higher in energy than the ground state.: its energy is higher than the energy of the ground state. When an atom in an excited state undergoes a transition to the ground state in a process called decay, it loses energy by emitting a photon whose energy corresponds to the difference in energy between the two states (Figure 6.11 "The Emission of Light by a Hydrogen Atom in an Excited State").

Figure 6.10 The Bohr Model of the Hydrogen Atom

(a) The distance of the orbit from the nucleus increases with increasing n. (b) The energy of the orbit becomes increasingly less negative with increasing n.

Figure 6.11 The Emission of Light by a Hydrogen Atom in an Excited State

(a) Light is emitted when the electron undergoes a transition from an orbit with a higher value of n (at a higher energy) to an orbit with a lower value of n (at lower energy). (b) The Balmer series of emission lines is due to transitions from orbits with n ≥ 3 to the orbit with n = 2. The differences in energy between these levels corresponds to light in the visible portion of the electromagnetic spectrum.

So the difference in energy (ΔE) between any two orbits or energy levels is given by $\Delta E=E_{n_1}-E_{n_2}\text{,}$ where n₁ is the final orbit and n₂ the initial orbit. Substituting from Bohr’s equation (Equation 6.9) for each energy value gives

If n₂ > n₁, the transition is from a higher energy state (larger-radius orbit) to a lower energy state (smaller-radius orbit), as shown by the dashed arrow in part (a) in Figure 6.11 "The Emission of Light by a Hydrogen Atom in an Excited State". Substituting hc/λ for ΔE gives

Canceling hc on both sides gives

Except for the negative sign, this is the same equation that Rydberg obtained experimentally. The negative sign in Equation 6.11 and Equation 6.12 indicates that energy is released as the electron moves from orbit n₂ to orbit n₁ because orbit n₂ is at a higher energy than orbit n₁. Bohr calculated the value of $ℛ$ independently and obtained a value of 1.0974 × 10⁷ m⁻¹, the same number Rydberg had obtained by analyzing the emission spectra.

We can now understand the physical basis for the Balmer series of lines in the emission spectrum of hydrogen (part (b) in Figure 6.9 "The Emission of Light by Hydrogen Atoms"). As shown in part (b) in Figure 6.11 "The Emission of Light by a Hydrogen Atom in an Excited State", the lines in this series correspond to transitions from higher-energy orbits (n > 2) to the second orbit (n = 2). Thus the hydrogen atoms in the sample have absorbed energy from the electrical discharge and decayed from a higher-energy excited state (n > 2) to a lower-energy state (n = 2) by emitting a photon of electromagnetic radiation whose energy corresponds exactly to the difference in energy between the two states (part (a) in Figure 6.11 "The Emission of Light by a Hydrogen Atom in an Excited State"). The n = 3 to n = 2 transition gives rise to the line at 656 nm (red), the n = 4 to n = 2 transition to the line at 486 nm (green), the n = 5 to n = 2 transition to the line at 434 nm (blue), and the n = 6 to n = 2 transition to the line at 410 nm (violet). Because a sample of hydrogen contains a large number of atoms, the intensity of the various lines in a line spectrum depends on the number of atoms in each excited state. At the temperature in the gas discharge tube, more atoms are in the n = 3 than the n ≥ 4 levels. Consequently, the n = 3 to n = 2 transition is the most intense line, producing the characteristic red color of a hydrogen discharge (part (a) in Figure 6.9 "The Emission of Light by Hydrogen Atoms"). Other families of lines are produced by transitions from excited states with n > 1 to the orbit with n = 1 or to orbits with n ≥ 3. These transitions are shown schematically in Figure 6.12 "Electron Transitions Responsible for the Various Series of Lines Observed in the Emission Spectrum of Hydrogen".

Figure 6.12 Electron Transitions Responsible for the Various Series of Lines Observed in the Emission Spectrum of Hydrogen

The Lyman series of lines is due to transitions from higher-energy orbits to the lowest-energy orbit (n = 1); these transitions release a great deal of energy, corresponding to radiation in the ultraviolet portion of the electromagnetic spectrum. The Paschen, Brackett, and Pfund series of lines are due to transitions from higher-energy orbits to orbits with n = 3, 4, and 5, respectively; these transitions release substantially less energy, corresponding to infrared radiation. (Orbits are not drawn to scale.)

In contemporary applications, electron transitions are used in timekeeping that needs to be exact. Telecommunications systems, such as cell phones, depend on timing signals that are accurate to within a millionth of a second per day, as are the devices that control the US power grid. Global positioning system (GPS) signals must be accurate to within a billionth of a second per day, which is equivalent to gaining or losing no more than one second in 1,400,000 years. Quantifying time requires finding an event with an interval that repeats on a regular basis. To achieve the accuracy required for modern purposes, physicists have turned to the atom. The current standard used to calibrate clocks is the cesium atom. Supercooled cesium atoms are placed in a vacuum chamber and bombarded with microwaves whose frequencies are carefully controlled. When the frequency is exactly right, the atoms absorb enough energy to undergo an electronic transition to a higher-energy state. Decay to a lower-energy state emits radiation. The microwave frequency is continually adjusted, serving as the clock’s pendulum. In 1967, the second was defined as the duration of 9,192,631,770 oscillations of the resonant frequency of a cesium atom, called the cesium clock. Research is currently under way to develop the next generation of atomic clocks that promise to be even more accurate. Such devices would allow scientists to monitor vanishingly faint electromagnetic signals produced by nerve pathways in the brain and geologists to measure variations in gravitational fields, which cause fluctuations in time, that would aid in the discovery of oil or minerals.

Bohr’s model of the hydrogen atom gave an exact explanation for its observed emission spectrum. The following are his key contributions to our understanding of atomic structure:

• Electrons can occupy only certain regions of space, called orbits.
• Orbits closer to the nucleus are lower in energy.
• Electrons can move from one orbit to another by absorbing or emitting energy, giving rise to characteristic spectra.

Unfortunately, Bohr could not explain why the electron should be restricted to particular orbits. Also, despite a great deal of tinkering, such as assuming that orbits could be ellipses rather than circles, his model could not quantitatively explain the emission spectra of any element other than hydrogen (Figure 6.13 "The Emission Spectra of Elements Compared with Hydrogen"). In fact, Bohr’s model worked only for species that contained just one electron: H, He⁺, Li²⁺, and so forth. Scientists needed a fundamental change in their way of thinking about the electronic structure of atoms to advance beyond the Bohr model.

Figure 6.13 The Emission Spectra of Elements Compared with Hydrogen

These images show (a) hydrogen gas, which is atomized to hydrogen atoms in the discharge tube; (b) neon; and (c) mercury.

Thus far we have explicitly considered only the emission of light by atoms in excited states, which produces an emission spectrumA spectrum produced by the emission of light by atoms in excited states.. The converse, absorption of light by ground-state atoms to produce an excited state, can also occur, producing an absorption spectrumA spectrum produced by the absorption of light by ground-state atoms.. Because each element has characteristic emission and absorption spectra, scientists can use such spectra to analyze the composition of matter, as we describe in Section 6.4 "The Relationship between Energy and Mass".

Applications of Emission and Absorption Spectra

If white light is passed through a sample of hydrogen, hydrogen atoms absorb energy as an electron is excited to higher energy levels (orbits with n ≥ 2). If the light that emerges is passed through a prism, it forms a continuous spectrum with black lines (corresponding to no light passing through the sample) at 656, 468, 434, and 410 nm. These wavelengths correspond to the n = 2 to n = 3, n = 2 to n = 4, n = 2 to n = 5, and n = 2 to n = 6 transitions. Any given element therefore has both a characteristic emission spectrum and a characteristic absorption spectrum, which are essentially complementary images.

Absorption of light by a hydrogen atom. (a) When a hydrogen atom absorbs a photon of light, an electron is excited to an orbit that has a higher energy and larger value of n. (b) Images of the emission and absorption spectra of hydrogen are shown here.

Emission and absorption spectra form the basis of spectroscopy, which uses spectra to provide information about the structure and the composition of a substance or an object. In particular, astronomers use emission and absorption spectra to determine the composition of stars and interstellar matter. As an example, consider the spectrum of sunlight shown in Figure 6.14 "The Visible Spectrum of Sunlight". Because the sun is very hot, the light it emits is in the form of a continuous emission spectrum. Superimposed on it, however, is a series of dark lines due primarily to the absorption of specific frequencies of light by cooler atoms in the outer atmosphere of the sun. By comparing these lines with the spectra of elements measured on Earth, we now know that the sun contains large amounts of hydrogen, iron, and carbon, along with smaller amounts of other elements. During the solar eclipse of 1868, the French astronomer Pierre Janssen (1824–1907) observed a set of lines that did not match those of any known element. He suggested that they were due to the presence of a new element, which he named helium, from the Greek helios, meaning “sun.” Helium was finally discovered in uranium ores on Earth in 1895.

Figure 6.14 The Visible Spectrum of Sunlight

The characteristic dark lines are mostly due to the absorption of light by elements that are present in the cooler outer part of the sun’s atmosphere; specific elements are indicated by the labels. The lines at 628 and 687 nm, however, are due to the absorption of light by oxygen molecules in Earth’s atmosphere.

The familiar red color of “neon” signs used in advertising is due to the emission spectrum of neon shown in part (b) in Figure 6.13 "The Emission Spectra of Elements Compared with Hydrogen". Similarly, the blue and yellow colors of certain street lights are caused, respectively, by mercury and sodium discharges. In all these cases, an electrical discharge excites neutral atoms to a higher energy state, and light is emitted when the atoms decay to the ground state. In the case of mercury, most of the emission lines are below 450 nm, which produces a blue light (part (c) in Figure 6.13 "The Emission Spectra of Elements Compared with Hydrogen"). In the case of sodium, the most intense emission lines are at 589 nm, which produces an intense yellow light.

Sodium and mercury spectra. Many street lights use bulbs that contain sodium or mercury vapor. Due to the very different emission spectra of these elements, they emit light of different colors.

The Chemistry of Fireworks

Figure 6.15 The Chemistry of Fireworks

(a) In the “multibreak” shell used for fireworks, the chambers contain mixtures of fuels and oxidizers plus compounds for special effects (“stars”) connected by time-delay fuses so that the chambers explode in stages. (b) The finale of a fireworks display usually consists of many shells fired simultaneously to give a dazzling multicolor display. The labels indicate the substances that are responsible for the colors of some of the fireworks shown.

The colors of fireworks are also due to atomic emission spectra. As shown in part (a) in Figure 6.15 "The Chemistry of Fireworks", a typical shell used in a fireworks display contains gunpowder to propel the shell into the air and a fuse to initiate a variety of redox reactions that produce heat and small explosions. Thermal energy excites the atoms to higher energy states; as they decay to lower energy states, the atoms emit light that gives the familiar colors. When oxidant/reductant mixtures listed in Table 6.2 "Common Chemicals Used in the Manufacture of Fireworks*" are ignited, a flash of white or yellow light is produced along with a loud bang. Achieving the colors shown in part (b) in Figure 6.15 "The Chemistry of Fireworks" requires adding a small amount of a substance that has an emission spectrum in the desired portion of the visible spectrum. For example, sodium is used for yellow because of its 589 nm emission lines. The intense yellow color of sodium would mask most other colors, so potassium and ammonium salts, rather than sodium salts, are usually used as oxidants to produce other colors, which explains the preponderance of such salts in Table 6.2 "Common Chemicals Used in the Manufacture of Fireworks*". Strontium salts, which are also used in highway flares, emit red light, whereas barium gives a green color. Blue is one of the most difficult colors to achieve. Copper(II) salts emit a pale blue light, but copper is dangerous to use because it forms highly unstable explosive compounds with anions such as chlorate. As you might guess, preparing fireworks with the desired properties is a complex, challenging, and potentially hazardous process.

Table 6.2 Common Chemicals Used in the Manufacture of Fireworks*

Oxidizers	Fuels (reductants)	Special effects
ammonium perchlorate	aluminum	blue flame: copper carbonate, copper sulfate, or copper oxide
barium chlorate	antimony sulfide	red flame: strontium nitrate or strontium carbonate
barium nitrate	charcoal	white flame: magnesium or aluminum
potassium chlorate	magnesium	yellow flame: sodium oxalate or cryolite (Na3AlF6)
potassium nitrate	sulfur	green flame: barium nitrate or barium chlorate
potassium perchlorate	titanium	white smoke: potassium nitrate plus sulfur
strontium nitrate		colored smoke: potassium chlorate and sulfur, plus organic dye
		whistling noise: potassium benzoate or sodium salicylate
		white sparks: aluminum, magnesium, or titanium
		gold sparks: iron fillings or charcoal
*Almost any combination of an oxidizer and a fuel may be used along with the compounds needed to produce a desired special effect.

Lasers

Most light emitted by atoms is polychromatic—containing more than one wavelength. In contrast, lasers (from light amplification by stimulated emission of radiation) emit monochromatic light—a single wavelength only. Lasers have many applications in fiber-optic telecommunications, the reading and recording of compact discs (CDs) and digital video discs (DVDs), steel cutting, and supermarket checkout scanners. Laser beams are generated by the same general phenomenon that gives rise to emission spectra, with one difference: only a single excited state is produced, which in principle results in only a single frequency of emitted light. In practice, however, inexpensive commercial lasers actually emit light with a very narrow range of wavelengths.

How a CD player uses a laser to read a CD. Inside a CD is a flat, light-reflecting layer called “land.” On the land are many “pits” recorded in a spiral-shaped track. (From the laser’s point of view, pits are actually the “bumps” shown here because the master disc with pits is duplicated negatively, turning the pits into bumps.) Pits have the same light-reflecting surface as land, but there are differences in the frequencies of the reflected light in the pit and the land, making light reflected by pits relatively dark compared with light reflected by land.

The operation of a ruby laser, the first type of laser used commercially, is shown schematically in Figure 6.16 "A Ruby Laser". Ruby is an impure form of aluminum oxide (Al₂O₃) in which Cr³⁺ replaces some of the Al³⁺ ions. The red color of the gem is caused by the absorption of light in the blue region of the visible spectrum by Cr³⁺ ions, which leaves only the longer wavelengths to be reflected back to the eye. One end of a ruby bar is coated with a fully reflecting mirror, and the mirror on the other end is only partially reflecting. When flashes of white light from a flash lamp excite the Cr³⁺ ions, they initially decay to a relatively long-lived excited state and can subsequently decay to the ground state by emitting a photon of red light. Some of these photons are reflected back and forth by the mirrored surfaces. As shown in part (b) in Figure 6.16 "A Ruby Laser", each time a photon interacts with an excited Cr³⁺ ion, it can stimulate that ion to emit another photon that has the same wavelength and is synchronized (in phase) with the first wave. This process produces a cascade of photons traveling back and forth, until the intense beam emerges through the partially reflecting mirror. Ruby is only one substance that is used to produce a laser; the choice of material determines the wavelength of light emitted, from infrared to ultraviolet, and the light output can be either continuous or pulsed.

Figure 6.16 A Ruby Laser

(a) This cutaway view of a ruby laser shows the ruby rod, the flash lamp used to excite the Cr³⁺ ions in the ruby, and the totally and partially reflective mirrors. (b) This schematic drawing illustrates how light from the flash lamp excites the Cr³⁺ ions to a short-lived excited state, which is followed by decay to a longer-lived excited state that is responsible for the stimulated in-phase emission of light by the laser.

When used in a DVD player or a CD player, light emitted by a laser passes through a transparent layer of plastic on the CD and is reflected by an underlying aluminum layer, which contains pits or flat regions that were created when the CD was recorded. Differences in the frequencies of the transmitted and reflected light are detected by light-sensitive equipment that converts these differences into binary code, a series of 1s and 0s, which is translated electronically into recognizable sounds and images.

Key Equation

Rydberg equation

Equation 6.8: $\frac{1}{\lambda }=ℛ\left(\frac{1}{n_1^2}-\frac{1}{n_2^2}\right)$

Summary

Atoms of individual elements emit light at only specific wavelengths, producing a line spectrum rather than the continuous spectrum of all wavelengths produced by a hot object. Niels Bohr explained the line spectrum of the hydrogen atom by assuming that the electron moved in circular orbits and that orbits with only certain radii were allowed. Lines in the spectrum were due to transitions in which an electron moved from a higher-energy orbit with a larger radius to a lower-energy orbit with smaller radius. The orbit closest to the nucleus represented the ground state of the atom and was most stable; orbits farther away were higher-energy excited states. Transitions from an excited state to a lower-energy state resulted in the emission of light with only a limited number of wavelengths. Bohr’s model could not, however, explain the spectra of atoms heavier than hydrogen.

Most light is polychromatic and contains light of many wavelengths. Light that has only a single wavelength is monochromatic and is produced by devices called lasers, which use transitions between two atomic energy levels to produce light in a very narrow range of wavelengths. Atoms can also absorb light of certain energies, resulting in a transition from the ground state or a lower-energy excited state to a higher-energy excited state. This produces an absorption spectrum, which has dark lines in the same position as the bright lines in the emission spectrum of an element.

Key Takeaway

• There is an intimate connection between the atomic structure of an atom and its spectral characteristics.

Conceptual Problems

1. Is the spectrum of the light emitted by isolated atoms of an element discrete or continuous? How do these spectra differ from those obtained by heating a bulk sample of a solid element? Explain your answers.

2. Explain why each element has a characteristic emission and absorption spectra. If spectral emissions had been found to be continuous rather than discrete, what would have been the implications for Bohr’s model of the atom?

3. Explain the differences between a ground state and an excited state. Describe what happens in the spectrum of a species when an electron moves from a ground state to an excited state. What happens in the spectrum when the electron falls from an excited state to a ground state?

4. What phenomenon causes a neon sign to have a characteristic color? If the emission spectrum of an element is constant, why do some neon signs have more than one color?

5. How is light from a laser different from the light emitted by a light source such as a light bulb? Describe how a laser produces light.

Numerical Problems

1. Using a Bohr model and the transition from n = 2 to n = 3 in an atom with a single electron, describe the mathematical relationship between an emission spectrum and an absorption spectrum. What is the energy of this transition? What does the sign of the energy value represent in this case? What range of light is associated with this transition?

2. If a hydrogen atom is excited from an n = 1 state to an n = 3 state, how much energy does this correspond to? Is this an absorption or an emission? What is the wavelength of the photon involved in this process? To what region of the electromagnetic spectrum does this correspond?

3. The hydrogen atom emits a photon with a 486 nm wavelength, corresponding to an electron decaying from the n = 4 level to which level? What is the color of the emission?

4. An electron in a hydrogen atom can decay from the n = 3 level to n = 2 level. What is the color of the emitted light? What is the energy of this transition?

5. Calculate the wavelength and energy of the photon that gives rise to the third line in order of increasing energy in the Lyman series in the emission spectrum of hydrogen. In what region of the spectrum does this wavelength occur? Describe qualitatively what the absorption spectrum looks like.

6. The wavelength of one of the lines in the Lyman series of hydrogen is 121 nm. In what region of the spectrum does this occur? To which electronic transition does this correspond?

7. The emission spectrum of helium is shown. What change in energy (ΔE) in kilojoules per mole gives rise to each line?

   

8. Removing an electron from solid potassium requires 222 kJ/mol. Would you expect to observe a photoelectric effect for potassium using a photon of blue light (λ = 485 nm)? What is the longest wavelength of energy capable of ejecting an electron from potassium? What is the corresponding color of light of this wavelength?

9. The binding energy of an electron is the energy needed to remove an electron from its lowest energy state. According to Bohr’s postulates, calculate the binding energy of an electron in a hydrogen atom in kilojoules per mole. What wavelength in nanometers is required to remove such an electron?

10. As a radio astronomer, you have observed spectral lines for hydrogen corresponding to a state with n = 320, and you would like to produce these lines in the laboratory. Is this feasible? Why or why not?

Answers

1. 656 nm; red light

3. n = 2, blue-green light

5. 97.2 nm, 2.04 × 10⁻¹⁸ J/photon, ultraviolet light, absorption spectrum is a single dark line at a wavelength of 97.2 nm

7. Violet: 390 nm, 307 kJ/mol photons; Blue-purple: 440 nm, 272 kJ/mol photons; Blue-green: 500 nm, 239 kJ/mol photons; Orange: 580 nm, 206 kJ/mol photons; Red: 650 nm, 184 kJ/mol photons

9. 1313 kJ/mol, λ ≤ 91.1 nm

The Wave Character of Matter

Einstein initially assumed that photons had zero mass, which made them a peculiar sort of particle indeed. In 1905, however, he published his special theory of relativity, which related energy and mass according to the following equation:

According to this theory, a photon of wavelength λ and frequency ν has a nonzero mass, which is given as follows:

That is, light, which had always been regarded as a wave, also has properties typical of particles, a condition known as wave–particle dualityA principle that matter and energy have properties typical of both waves and particles.. Depending on conditions, light could be viewed as either a wave or a particle.

In 1922, the American physicist Arthur Compton (1892–1962) reported the results of experiments involving the collision of x-rays and electrons that supported the particle nature of light. At about the same time, a young French physics student, Louis de Broglie (1892–1972), began to wonder whether the converse was true: Could particles exhibit the properties of waves? In his PhD dissertation submitted to the Sorbonne in 1924, de Broglie proposed that a particle such as an electron could be described by a wave whose wavelength is given by

where h is Planck’s constant, m is the mass of the particle, and v is the velocity of the particle. This revolutionary idea was quickly confirmed by American physicists Clinton Davisson (1881–1958) and Lester Germer (1896–1971), who showed that beams of electrons, regarded as particles, were diffracted by a sodium chloride crystal in the same manner as x-rays, which were regarded as waves. It was proven experimentally that electrons do exhibit the properties of waves. For his work, de Broglie received the Nobel Prize in Physics in 1929.

If particles exhibit the properties of waves, why had no one observed them before? The answer lies in the numerator of de Broglie’s equation, which is an extremely small number. As you will calculate in Example 4, Planck’s constant (6.63 × 10⁻³⁴ J·s) is so small that the wavelength of a particle with a large mass is too short (less than the diameter of an atomic nucleus) to be noticeable.

As you calculated in Example 4, objects such as a baseball or a neutron have such short wavelengths that they are best regarded primarily as particles. In contrast, objects with very small masses (such as photons) have large wavelengths and can be viewed primarily as waves. Objects with intermediate masses, such as electrons, exhibit the properties of both particles and waves. Although we still usually think of electrons as particles, the wave nature of electrons is employed in an electron microscope, which has revealed most of what we know about the microscopic structure of living organisms and materials. Because the wavelength of an electron beam is much shorter than the wavelength of a beam of visible light, this instrument can resolve smaller details than a light microscope can (Figure 6.17 "A Comparison of Images Obtained Using a Light Microscope and an Electron Microscope").

Figure 6.17 A Comparison of Images Obtained Using a Light Microscope and an Electron Microscope

Because of their shorter wavelength, high-energy electrons have a higher resolving power than visible light. Consequently, an electron microscope (b) is able to resolve finer details than a light microscope (a). (Radiolaria, which are shown here, are unicellular planktonic organisms.)

Standing Waves

De Broglie also investigated why only certain orbits were allowed in Bohr’s model of the hydrogen atom. He hypothesized that the electron behaves like a standing waveA wave that does not travel in space., a wave that does not travel in space. An example of a standing wave is the motion of a string of a violin or guitar. When the string is plucked, it vibrates at certain fixed frequencies because it is fastened at both ends (Figure 6.18 "Standing Waves on a Vibrating String"). If the length of the string is L, then the lowest-energy vibration (the fundamentalThe lowest-energy standing wave.) has wavelength

Higher-energy vibrations (overtonesThe vibration of a standing wave that is higher in energy than the fundamental vibration.) are produced when the string is plucked more strongly; they have wavelengths given by

where n has any integral value. Thus the vibrational energy of the string is quantized, and only certain wavelengths and frequencies are possible. Notice in Figure 6.18 "Standing Waves on a Vibrating String" that all overtones have one or more nodesThe point where the amplitude of a wave is zero., points where the string does not move. The amplitude of the wave at a node is zero.

Figure 6.18 Standing Waves on a Vibrating String

The vibration with n = 1 is the fundamental and contains no nodes. Vibrations with higher values of n are called overtones; they contain n − 1 nodes.

Quantized vibrations and overtones containing nodes are not restricted to one-dimensional systems, such as strings. A two-dimensional surface, such as a drumhead, also has quantized vibrations. Similarly, when the ends of a string are joined to form a circle, the only allowed vibrations are those with wavelength

where r is the radius of the circle. De Broglie argued that Bohr’s allowed orbits could be understood if the electron behaved like a standing circular wave (Figure 6.19 "Standing Circular Wave and Destructive Interference"). The standing wave could exist only if the circumference of the circle was an integral multiple of the wavelength such that the propagated waves were all in phase, thereby increasing the net amplitudes and causing constructive interference. Otherwise, the propagated waves would be out of phase, resulting in a net decrease in amplitude and causing destructive interference. De Broglie’s idea explained Bohr’s allowed orbits and energy levels nicely: in the lowest energy level, corresponding to n = 1 in Equation 6.18, one complete wavelength would close the circle. Higher energy levels would have successively higher values of n with a corresponding number of nodes.

Standing waves are often observed on rivers, reservoirs, ponds, and lakes when seismic waves from an earthquake travel through the area. The waves are called seismic seiches, a term first used in 1955 when lake levels in England and Norway oscillated from side to side as a result of the Assam earthquake of 1950 in Tibet. They were first described in the Proceedings of the Royal Society in 1755 when they were seen in English harbors and ponds after a large earthquake in Lisbon, Portugal. Seismic seiches were also observed in many places in North America after the Alaska earthquake of March 28, 1964. Those occurring in western reservoirs lasted for two hours or longer, and amplitudes reached as high as nearly 6 ft along the Gulf Coast. The height of seiches is approximately proportional to the thickness of surface sediments; a deeper channel will produce a higher seiche.

Figure 6.19 Standing Circular Wave and Destructive Interference

(a) In a standing circular wave with n = 5, the circumference of the circle corresponds to exactly five wavelengths, which results in constructive interference of the wave with itself when overlapping occurs. (b) If the circumference of the circle is not equal to an integral multiple of wavelengths, then the wave does not overlap exactly with itself, and the resulting destructive interference will result in cancellation of the wave. Consequently, a standing wave cannot exist under these conditions.

As you will see, several of de Broglie’s ideas are retained in the modern theory of the electronic structure of the atom: the wave behavior of the electron, the concept of standing waves, and the presence of nodes that increase in number as the energy level increases. Unfortunately, his explanation also contains one major feature that we know to be incorrect: in the currently accepted model, the electron in a given orbit is not always at the same distance from the nucleus.

The Heisenberg Uncertainty Principle

Because a wave is a disturbance that travels in space, it has no fixed position. One might therefore expect that it would also be hard to specify the exact position of a particle that exhibits wavelike behavior. This situation was described mathematically by the German physicist Werner Heisenberg (1901–1976; Nobel Prize in Physics, 1932), who related the position of a particle to its momentum. Referring to the electron, Heisenberg stated that “at every moment the electron has only an inaccurate position and an inaccurate velocity, and between these two inaccuracies there is this uncertainty relation.” Mathematically, the Heisenberg uncertainty principleA principle stating that the uncertainty in the position of a particle $(\Delta x)$ multiplied by the uncertainty in its momentum $[\Delta (mv)]$ is greater than or equal to Planck’s constant $(h)$ divided by 4π: $\Delta x[\Delta (mv)]\ge h/4\pi .$ states that the uncertainty in the position of a particle (Δx) multiplied by the uncertainty in its momentum [Δ(mv)] is greater than or equal to Planck’s constant divided by 4π:

Because Planck’s constant is a very small number, the Heisenberg uncertainty principle is important only for particles such as electrons that have very low masses. These are the same particles predicted by de Broglie’s equation to have measurable wavelengths.

If the precise position x of a particle is known absolutely (Δx = 0), then the uncertainty in its momentum must be infinite:

Because the mass of the electron at rest (m) is both constant and accurately known, the uncertainty in Δ(mv) must be due to the Δv term, which would have to be infinitely large for Δ(mv) to equal infinity. That is, according to Equation 6.20, the more accurately we know the exact position of the electron (as Δx → 0), the less accurately we know the speed and the kinetic energy of the electron (1/2 mv²) because Δ(mv) → ∞. Conversely, the more accurately we know the precise momentum (and the energy) of the electron [as Δ(mv) → 0], then Δx → ∞ and we have no idea where the electron is.

Bohr’s model of the hydrogen atom violated the Heisenberg uncertainty principle by trying to specify simultaneously both the position (an orbit of a particular radius) and the energy (a quantity related to the momentum) of the electron. Moreover, given its mass and wavelike nature, the electron in the hydrogen atom could not possibly orbit the nucleus in a well-defined circular path as predicted by Bohr. You will see, however, that the most probable radius of the electron in the hydrogen atom is exactly the one predicted by Bohr’s model.

Wave Functions

A wave function (Ψ)A mathematical function that relates the location of an electron at a given point in space to the amplitude of its wave, which corresponds to its energy.Ψ is the uppercase Greek psi. is a mathematical function that relates the location of an electron at a given point in space (identified by x, y, and z coordinates) to the amplitude of its wave, which corresponds to its energy. Thus each wave function is associated with a particular energy E. The properties of wave functions derived from quantum mechanics are summarized here:

• A wave function uses three variables to describe the position of an electron. A fourth variable is usually required to fully describe the location of objects in motion. Three specify the position in space (as with the Cartesian coordinates x, y, and z), and one specifies the time at which the object is at the specified location. For example, if you wanted to intercept an enemy submarine, you would need to know its latitude, longitude, and depth, as well as the time at which it was going to be at this position (Figure 6.20 "The Four Variables (Latitude, Longitude, Depth, and Time) Required to Precisely Locate an Object"). For electrons, we can ignore the time dependence because we will be using standing waves, which by definition do not change with time, to describe the position of an electron.

Figure 6.20 The Four Variables (Latitude, Longitude, Depth, and Time) Required to Precisely Locate an Object

If you are the captain of a ship trying to intercept an enemy submarine, you need to deliver your depth charge to the right location at the right time.

• The magnitude of the wave function at a particular point in space is proportional to the amplitude of the wave at that point. Many wave functions are complex functions, which is a mathematical term indicating that they contain $\sqrt{-1}$, represented as i. Hence the amplitude of the wave has no real physical significance. In contrast, the sign of the wave function (either positive or negative) corresponds to the phase of the wave, which will be important in our discussion of chemical bonding in Chapter 9 "Molecular Geometry and Covalent Bonding Models". The sign of the wave function should not be confused with a positive or negative electrical charge.
• The square of the wave function at a given point is proportional to the probability of finding an electron at that point, which leads to a distribution of probabilities in space. The square of the wave function (Ψ²) is always a real quantity [recall that ${(\sqrt{-1})}^2=-1$] that is proportional to the probability of finding an electron at a given point.More accurately, the probability is given by the product of the wave function Ψ and its complex conjugate Ψ*, in which all terms that contain i are replaced by −i. We use probabilities because, according to Heisenberg’s uncertainty principle, we cannot precisely specify the position of an electron. The probability of finding an electron at any point in space depends on several factors, including the distance from the nucleus and, in many cases, the atomic equivalent of latitude and longitude. As one way of graphically representing the probability distribution, the probability of finding an electron is indicated by the density of colored dots, as shown for the ground state of the hydrogen atom in Figure 6.21 "Probability of Finding the Electron in the Ground State of the Hydrogen Atom at Different Points in Space".

Figure 6.21 Probability of Finding the Electron in the Ground State of the Hydrogen Atom at Different Points in Space

(a) The density of the dots shows electron probability. (b) In this plot of Ψ² versus r for the ground state of the hydrogen atom, the electron probability density is greatest at r = 0 (the nucleus) and falls off with increasing r. Because the line never actually reaches the horizontal axis, the probability of finding the electron at very large values of r is very small but not zero.

• Describing the electron distribution as a standing wave leads to sets of quantum numbers that are characteristic of each wave function. From the patterns of one- and two-dimensional standing waves shown in Figure 6.18 "Standing Waves on a Vibrating String" and Figure 6.19 "Standing Circular Wave and Destructive Interference", you might expect (correctly) that the patterns of three-dimensional standing waves would be complex. Fortunately, however, in the 18th century, a French mathematician, Adrien Legendre (1752–1783), developed a set of equations to describe the motion of tidal waves on the surface of a flooded planet. Schrödinger incorporated Legendre’s equations into his wave functions. The requirement that the waves must be in phase with one another to avoid cancellation and produce a standing wave results in a limited number of solutions (wave functions), each of which is specified by a set of numbers called quantum numbersA unique set of numbers that specifies a wave function (a solution to the Schrödinger equation), which provides important information about the energy and spatial distribution of an electron..
• Each wave function is associated with a particular energy. As in Bohr’s model, the energy of an electron in an atom is quantized; it can have only certain allowed values. The major difference between Bohr’s model and Schrödinger’s approach is that Bohr had to impose the idea of quantization arbitrarily, whereas in Schrödinger’s approach, quantization is a natural consequence of describing an electron as a standing wave.

Quantum Numbers

Schrödinger’s approach uses three quantum numbers (n, l, and m_l) to specify any wave function. The quantum numbers provide information about the spatial distribution of an electron. Although n can be any positive integer, only certain values of l and m_l are allowed for a given value of n.

Orbital Shapes

An orbital is the quantum mechanical refinement of Bohr’s orbit. In contrast to his concept of a simple circular orbit with a fixed radius, orbitals are mathematically derived regions of space with different probabilities of having an electron.

One way of representing electron probability distributions was illustrated in Figure 6.21 "Probability of Finding the Electron in the Ground State of the Hydrogen Atom at Different Points in Space" for the 1s orbital of hydrogen. Because Ψ² gives the probability of finding an electron in a given volume of space (such as a cubic picometer), a plot of Ψ² versus distance from the nucleus (r) is a plot of the probability density. The 1s orbital is spherically symmetrical, so the probability of finding a 1s electron at any given point depends only on its distance from the nucleus. The probability density is greatest at r = 0 (at the nucleus) and decreases steadily with increasing distance. At very large values of r, the electron probability density is very small but not zero.

In contrast, we can calculate the radial probability (the probability of finding a 1s electron at a distance r from the nucleus) by adding together the probabilities of an electron being at all points on a series of x spherical shells of radius r₁, r₂, r₃,…, r_{x − 1}, r_x. In effect, we are dividing the atom into very thin concentric shells, much like the layers of an onion (part (a) in Figure 6.22 "Most Probable Radius for the Electron in the Ground State of the Hydrogen Atom"), and calculating the probability of finding an electron on each spherical shell. Recall that the electron probability density is greatest at r = 0 (part (b) in Figure 6.22 "Most Probable Radius for the Electron in the Ground State of the Hydrogen Atom"), so the density of dots is greatest for the smallest spherical shells in part (a) in Figure 6.22 "Most Probable Radius for the Electron in the Ground State of the Hydrogen Atom". In contrast, the surface area of each spherical shell is equal to 4πr², which increases very rapidly with increasing r (part (c) in Figure 6.22 "Most Probable Radius for the Electron in the Ground State of the Hydrogen Atom"). Because the surface area of the spherical shells increases more rapidly with increasing r than the electron probability density decreases, the plot of radial probability has a maximum at a particular distance (part (d) in Figure 6.22 "Most Probable Radius for the Electron in the Ground State of the Hydrogen Atom"). Most important, when r is very small, the surface area of a spherical shell is so small that the total probability of finding an electron close to the nucleus is very low; at the nucleus, the electron probability vanishes (part (d) in Figure 6.22 "Most Probable Radius for the Electron in the Ground State of the Hydrogen Atom").

Figure 6.22 Most Probable Radius for the Electron in the Ground State of the Hydrogen Atom

(a) Imagine dividing the atom’s total volume into very thin concentric shells as shown in the onion drawing. (b) A plot of electron probability density Ψ² versus r shows that the electron probability density is greatest at r = 0 and falls off smoothly with increasing r. The density of the dots is therefore greatest in the innermost shells of the onion. (c) The surface area of each shell, given by 4πr², increases rapidly with increasing r. (d) If we count the number of dots in each spherical shell, we obtain the total probability of finding the electron at a given value of r. Because the surface area of each shell increases more rapidly with increasing r than the electron probability density decreases, a plot of electron probability versus r (the radial probability) shows a peak. This peak corresponds to the most probable radius for the electron, 52.9 pm, which is exactly the radius predicted by Bohr’s model of the hydrogen atom.

For the hydrogen atom, the peak in the radial probability plot occurs at r = 0.529 Å (52.9 pm), which is exactly the radius calculated by Bohr for the n = 1 orbit. Thus the most probable radius obtained from quantum mechanics is identical to the radius calculated by classical mechanics. In Bohr’s model, however, the electron was assumed to be at this distance 100% of the time, whereas in the Schrödinger model, it is at this distance only some of the time. The difference between the two models is attributable to the wavelike behavior of the electron and the Heisenberg uncertainty principle.

Figure 6.23 "Probability Densities for the 1" compares the electron probability densities for the hydrogen 1s, 2s, and 3s orbitals. Note that all three are spherically symmetrical. For the 2s and 3s orbitals, however (and for all other s orbitals as well), the electron probability density does not fall off smoothly with increasing r. Instead, a series of minima and maxima are observed in the radial probability plots (part (c) in Figure 6.23 "Probability Densities for the 1"). The minima correspond to spherical nodes (regions of zero electron probability), which alternate with spherical regions of nonzero electron probability.

Figure 6.23 Probability Densities for the 1s, 2s, and 3s Orbitals of the Hydrogen Atom

(a) The electron probability density in any plane that contains the nucleus is shown. Note the presence of circular regions, or nodes, where the probability density is zero. (b) Contour surfaces enclose 90% of the electron probability, which illustrates the different sizes of the 1s, 2s, and 3s orbitals. The cutaway drawings give partial views of the internal spherical nodes. The orange color corresponds to regions of space where the phase of the wave function is positive, and the blue color corresponds to regions of space where the phase of the wave function is negative. (c) In these plots of electron probability as a function of distance from the nucleus (r) in all directions (radial probability), the most probable radius increases as n increases, but the 2s and 3s orbitals have regions of significant electron probability at small values of r.

p Orbitals

Only s orbitals are spherically symmetrical. As the value of l increases, the number of orbitals in a given subshell increases, and the shapes of the orbitals become more complex. Because the 2p subshell has l = 1, with three values of m_l (−1, 0, and +1), there are three 2p orbitals.

Figure 6.24 Electron Probability Distribution for a Hydrogen 2p Orbital

The nodal plane of zero electron density separates the two lobes of the 2p orbital. As in Figure 6.23 "Probability Densities for the 1", the colors correspond to regions of space where the phase of the wave function is positive (orange) and negative (blue).

The electron probability distribution for one of the hydrogen 2p orbitals is shown in Figure 6.24 "Electron Probability Distribution for a Hydrogen 2". Because this orbital has two lobes of electron density arranged along the z axis, with an electron density of zero in the xy plane (i.e., the xy plane is a nodal plane), it is a 2p_z orbital. As shown in Figure 6.25 "The Three Equivalent 2", the other two 2p orbitals have identical shapes, but they lie along the x axis (2p_x) and y axis (2p_y), respectively. Note that each p orbital has just one nodal plane. In each case, the phase of the wave function for each of the 2p orbitals is positive for the lobe that points along the positive axis and negative for the lobe that points along the negative axis. It is important to emphasize that these signs correspond to the phase of the wave that describes the electron motion, not to positive or negative charges.

Figure 6.25 The Three Equivalent 2p Orbitals of the Hydrogen Atom

The surfaces shown enclose 90% of the total electron probability for the 2p_x, 2p_y, and 2p_z orbitals. Each orbital is oriented along the axis indicated by the subscript and a nodal plane that is perpendicular to that axis bisects each 2p orbital. The phase of the wave function is positive (orange) in the region of space where x, y, or z is positive and negative (blue) where x, y, or z is negative.

Just as with the s orbitals, the size and complexity of the p orbitals for any atom increase as the principal quantum number n increases. The shapes of the 90% probability surfaces of the 3p, 4p, and higher-energy p orbitals are, however, essentially the same as those shown in Figure 6.25 "The Three Equivalent 2".

d Orbitals

Subshells with l = 2 have five d orbitals; the first principal shell to have a d subshell corresponds to n = 3. The five d orbitals have m_l values of −2, −1, 0, +1, and +2.

Figure 6.26 The Five Equivalent 3d Orbitals of the Hydrogen Atom

The surfaces shown enclose 90% of the total electron probability for the five hydrogen 3d orbitals. Four of the five 3d orbitals consist of four lobes arranged in a plane that is intersected by two perpendicular nodal planes. These four orbitals have the same shape but different orientations. The fifth 3d orbital, $3d_{z^2}$, has a distinct shape even though it is mathematically equivalent to the others. The phase of the wave function for the different lobes is indicated by color: orange for positive and blue for negative.

The hydrogen 3d orbitals, shown in Figure 6.26 "The Five Equivalent 3", have more complex shapes than the 2p orbitals. All five 3d orbitals contain two nodal surfaces, as compared to one for each p orbital and zero for each s orbital. In three of the d orbitals, the lobes of electron density are oriented between the x and y, x and z, and y and z planes; these orbitals are referred to as the 3d_xy, 3d_xz, and 3d_yz orbitals, respectively. A fourth d orbital has lobes lying along the x and y axes; this is the $3d_{x^2-y^2}$ orbital. The fifth 3d orbital, called the $3d_{z^2}$ orbital, has a unique shape: it looks like a 2p_z orbital combined with an additional doughnut of electron probability lying in the xy plane. Despite its peculiar shape, the $3d_{z^2}$ orbital is mathematically equivalent to the other four and has the same energy. In contrast to p orbitals, the phase of the wave function for d orbitals is the same for opposite pairs of lobes. As shown in Figure 6.26 "The Five Equivalent 3", the phase of the wave function is positive for the two lobes of the $d_{z^2}$ orbital that lie along the z axis, whereas the phase of the wave function is negative for the doughnut of electron density in the xy plane. Like the s and p orbitals, as n increases, the size of the d orbitals increases, but the overall shapes remain similar to those depicted in Figure 6.26 "The Five Equivalent 3".

Orbital Energies

Although we have discussed the shapes of orbitals, we have said little about their comparative energies. We begin our discussion of orbital energiesA particular energy associated with a given set of quantum numbers. by considering atoms or ions with only a single electron (such as H or He⁺).

The relative energies of the atomic orbitals with n ≤ 4 for a hydrogen atom are plotted in Figure 6.27 "Orbital Energy Level Diagram for the Hydrogen Atom"; note that the orbital energies depend on only the principal quantum number n. Consequently, the energies of the 2s and 2p orbitals of hydrogen are the same; the energies of the 3s, 3p, and 3d orbitals are the same; and so forth. The orbital energies obtained for hydrogen using quantum mechanics are exactly the same as the allowed energies calculated by Bohr. In contrast to Bohr’s model, however, which allowed only one orbit for each energy level, quantum mechanics predicts that there are 4 orbitals with different electron density distributions in the n = 2 principal shell (one 2s and three 2p orbitals), 9 in the n = 3 principal shell, and 16 in the n = 4 principal shell.The different values of l and m_l for the individual orbitals within a given principal shell are not important for understanding the emission or absorption spectra of the hydrogen atom under most conditions, but they do explain the splittings of the main lines that are observed when hydrogen atoms are placed in a magnetic field. As we have just seen, however, quantum mechanics also predicts that in the hydrogen atom, all orbitals with the same value of n (e.g., the three 2p orbitals) are degenerateHaving the same energy., meaning that they have the same energy. Figure 6.27 "Orbital Energy Level Diagram for the Hydrogen Atom" shows that the energy levels become closer and closer together as the value of n increases, as expected because of the 1/n² dependence of orbital energies.

Figure 6.27 Orbital Energy Level Diagram for the Hydrogen Atom

Each box corresponds to one orbital. Note that the difference in energy between orbitals decreases rapidly with increasing values of n.

The energies of the orbitals in any species with only one electron can be calculated by a minor variation of Bohr’s equation (Equation 6.9), which can be extended to other single-electron species by incorporating the nuclear charge Z (the number of protons in the nucleus):

In general, both energy and radius decrease as the nuclear charge increases. Thus the most stable orbitals (those with the lowest energy) are those closest to the nucleus. For example, in the ground state of the hydrogen atom, the single electron is in the 1s orbital, whereas in the first excited state, the atom has absorbed energy and the electron has been promoted to one of the n = 2 orbitals. In ions with only a single electron, the energy of a given orbital depends on only n, and all subshells within a principal shell, such as the p_x, p_y, and p_z orbitals, are degenerate.

Effective Nuclear Charges

For an atom or an ion with only a single electron, we can calculate the potential energy by considering only the electrostatic attraction between the positively charged nucleus and the negatively charged electron. When more than one electron is present, however, the total energy of the atom or the ion depends not only on attractive electron-nucleus interactions but also on repulsive electron-electron interactions. When there are two electrons, the repulsive interactions depend on the positions of both electrons at a given instant, but because we cannot specify the exact positions of the electrons, it is impossible to exactly calculate the repulsive interactions. Consequently, we must use approximate methods to deal with the effect of electron-electron repulsions on orbital energies.

If an electron is far from the nucleus (i.e., if the distance r between the nucleus and the electron is large), then at any given moment, most of the other electrons will be between that electron and the nucleus. Hence the electrons will cancel a portion of the positive charge of the nucleus and thereby decrease the attractive interaction between it and the electron farther away. As a result, the electron farther away experiences an effective nuclear charge (Z_eff)The nuclear charge an electron actually experiences because of shielding from other electrons closer to the nucleus. that is less than the actual nuclear charge Z. This effect is called electron shieldingThe effect by which electrons closer to the nucleus neutralize a portion of the positive charge of the nucleus and thereby decrease the attractive interaction between the nucleus and an electron father away.. As the distance between an electron and the nucleus approaches infinity, Z_eff approaches a value of 1 because all the other (Z − 1) electrons in the neutral atom are, on the average, between it and the nucleus. If, on the other hand, an electron is very close to the nucleus, then at any given moment most of the other electrons are farther from the nucleus and do not shield the nuclear charge. At r ≈ 0, the positive charge experienced by an electron is approximately the full nuclear charge, or Z_eff ≈ Z. At intermediate values of r, the effective nuclear charge is somewhere between 1 and Z: 1 ≤ Z_eff ≤ Z. Thus the actual Z_eff experienced by an electron in a given orbital depends not only on the spatial distribution of the electron in that orbital but also on the distribution of all the other electrons present. This leads to large differences in Z_eff for different elements, as shown in Figure 6.28 "Relationship between the Effective Nuclear Charge " for the elements of the first three rows of the periodic table. Notice that only for hydrogen does Z_eff = Z, and only for helium are Z_eff and Z comparable in magnitude.

Figure 6.28 Relationship between the Effective Nuclear Charge Z_eff and the Atomic Number Z for the Outer Electrons of the Elements of the First Three Rows of the Periodic Table

Except for hydrogen, Z_eff is always less than Z, and Z_eff increases from left to right as you go across a row.

The energies of the different orbitals for a typical multielectron atom are shown in Figure 6.29 "Orbital Energy Level Diagram for a Typical Multielectron Atom". Within a given principal shell of a multielectron atom, the orbital energies increase with increasing l. An ns orbital always lies below the corresponding np orbital, which in turn lies below the nd orbital. These energy differences are caused by the effects of shielding and penetration, the extent to which a given orbital lies inside other filled orbitals. As shown in Figure 6.30 "Orbital Penetration", for example, an electron in the 2s orbital penetrates inside a filled 1s orbital more than an electron in a 2p orbital does. Hence in an atom with a filled 1s orbital, the Z_eff experienced by a 2s electron is greater than the Z_eff experienced by a 2p electron. Consequently, the 2s electron is more tightly bound to the nucleus and has a lower energy, consistent with the order of energies shown in Figure 6.29 "Orbital Energy Level Diagram for a Typical Multielectron Atom".

Figure 6.29 Orbital Energy Level Diagram for a Typical Multielectron Atom

Because of the effects of shielding and the different radial distributions of orbitals with the same value of n but different values of l, the different subshells are not degenerate in a multielectron atom. (Compare this with Figure 6.27 "Orbital Energy Level Diagram for the Hydrogen Atom".) For a given value of n, the ns orbital is always lower in energy than the np orbitals, which are lower in energy than the nd orbitals, and so forth. As a result, some subshells with higher principal quantum numbers are actually lower in energy than subshells with a lower value of n; for example, the 4s orbital is lower in energy than the 3d orbitals for most atoms.

Figure 6.30 Orbital Penetration

A comparison of the radial probability distribution of the 2s and 2p orbitals for various states of the hydrogen atom shows that the 2s orbital penetrates inside the 1s orbital more than the 2p orbital does. Consequently, when an electron is in the small inner lobe of the 2s orbital, it experiences a relatively large value of Z_eff, which causes the energy of the 2s orbital to be lower than the energy of the 2p orbital.

Notice in Figure 6.29 "Orbital Energy Level Diagram for a Typical Multielectron Atom" that the difference in energies between subshells can be so large that the energies of orbitals from different principal shells can become approximately equal. For example, the energy of the 3d orbitals in most atoms is actually between the energies of the 4s and the 4p orbitals.

Electron Spin: The Fourth Quantum Number

When scientists analyzed the emission and absorption spectra of the elements more closely, they saw that for elements having more than one electron, nearly all the lines in the spectra were actually pairs of very closely spaced lines. Because each line represents an energy level available to electrons in the atom, there are twice as many energy levels available as would be predicted solely based on the quantum numbers n, l, and m_l. Scientists also discovered that applying a magnetic field caused the lines in the pairs to split farther apart. In 1925, two graduate students in physics in the Netherlands, George Uhlenbeck (1900–1988) and Samuel Goudsmit (1902–1978), proposed that the splittings were caused by an electron spinning about its axis, much as Earth spins about its axis. When an electrically charged object spins, it produces a magnetic moment parallel to the axis of rotation, making it behave like a magnet. Although the electron cannot be viewed solely as a particle, spinning or otherwise, it is indisputable that it does have a magnetic moment. This magnetic moment is called electron spinThe magnetic moment that results when an electron spins. Electrons have two possible orientations (spin up and spin down), which are described by a fourth quantum number (m_s)..

Figure 6.31 Electron Spin

In a magnetic field, an electron has two possible orientations with different energies, one with spin up, aligned with the magnetic field, and one with spin down, aligned against it. All other orientations are forbidden.

In an external magnetic field, the electron has two possible orientations (Figure 6.31 "Electron Spin"). These are described by a fourth quantum number (m_s), which for any electron can have only two possible values, designated +½ (up) and −½ (down) to indicate that the two orientations are opposites; the subscript s is for spin. An electron behaves like a magnet that has one of two possible orientations, aligned either with the magnetic field or against it.

The Pauli Principle

The implications of electron spin for chemistry were recognized almost immediately by an Austrian physicist,Wolfgang Pauli (1900–1958; Nobel Prize in Physics, 1945), who determined that each orbital can contain no more than two electrons. He developed the Pauli exclusion principleA principle stating that no two electrons in an atom can have the same value of all four quantum numbers.: No two electrons in an atom can have the same values of all four quantum numbers (n, l, m_l, m_s).

By giving the values of n, l, and m_l, we also specify a particular orbital (e.g., 1s with n = 1, l = 0, m_l = 0). Because m_s has only two possible values (+½ or −½), two electrons, and only two electrons, can occupy any given orbital, one with spin up and one with spin down. With this information, we can proceed to construct the entire periodic table, which, as you learned in Chapter 1 "Introduction to Chemistry", was originally based on the physical and chemical properties of the known elements.

Electron Configurations of the Elements

The electron configurationThe arrangement of an element’s electrons in its atomic orbitals. of an element is the arrangement of its electrons in its atomic orbitals. By knowing the electron configuration of an element, we can predict and explain a great deal of its chemistry.

The Aufbau Principle

We construct the periodic table by following the aufbau principleThe process used to build up the periodic table by adding protons one by one to the nucleus and adding the corresponding electrons to the lowest-energy orbital available without violating the Pauli exclusion principle. (from German, meaning “building up”). First we determine the number of electrons in the atom; then we add electrons one at a time to the lowest-energy orbital available without violating the Pauli principle. We use the orbital energy diagram of Figure 6.29 "Orbital Energy Level Diagram for a Typical Multielectron Atom", recognizing that each orbital can hold two electrons, one with spin up ↑, corresponding to m_s = +½, which is arbitrarily written first, and one with spin down ↓, corresponding to m_s = −½. A filled orbital is indicated by ↑↓, in which the electron spins are said to be paired. Here is a schematic orbital diagram for a hydrogen atom in its ground state:

From the orbital diagram, we can write the electron configuration in an abbreviated form in which the occupied orbitals are identified by their principal quantum number n and their value of l (s, p, d, or f), with the number of electrons in the subshell indicated by a superscript. For hydrogen, therefore, the single electron is placed in the 1s orbital, which is the orbital lowest in energy (Figure 6.29 "Orbital Energy Level Diagram for a Typical Multielectron Atom"), and the electron configuration is written as 1s¹ and read as “one-s-one.”

A neutral helium atom, with an atomic number of 2 (Z = 2), has two electrons. We place one electron in the orbital that is lowest in energy, the 1s orbital. From the Pauli exclusion principle, we know that an orbital can contain two electrons with opposite spin, so we place the second electron in the same orbital as the first but pointing down, so that the electrons are paired. The orbital diagram for the helium atom is therefore

written as 1s², where the superscript 2 implies the pairing of spins. Otherwise, our configuration would violate the Pauli principle.

The next element is lithium, with Z = 3 and three electrons in the neutral atom. We know that the 1s orbital can hold two of the electrons with their spins paired. Figure 6.29 "Orbital Energy Level Diagram for a Typical Multielectron Atom" tells us that the next lowest energy orbital is 2s, so the orbital diagram for lithium is

This electron configuration is written as 1s²2s¹.

The next element is beryllium, with Z = 4 and four electrons. We fill both the 1s and 2s orbitals to achieve a 1s²2s² electron configuration:

When we reach boron, with Z = 5 and five electrons, we must place the fifth electron in one of the 2p orbitals. Because all three 2p orbitals are degenerate, it doesn’t matter which one we select. The electron configuration of boron is 1s²2s²2p¹:

At carbon, with Z = 6 and six electrons, we are faced with a choice. Should the sixth electron be placed in the same 2p orbital that already has an electron, or should it go in one of the empty 2p orbitals? If it goes in an empty 2p orbital, will the sixth electron have its spin aligned with or be opposite to the spin of the fifth? In short, which of the following three orbital diagrams is correct for carbon, remembering that the 2p orbitals are degenerate?

Because of electron-electron repulsions, it is more favorable energetically for an electron to be in an unoccupied orbital than in one that is already occupied; hence we can eliminate choice a. Similarly, experiments have shown that choice b is slightly higher in energy (less stable) than choice c because electrons in degenerate orbitals prefer to line up with their spins parallel; thus, we can eliminate choice b. Choice c illustrates Hund’s ruleA rule stating that the lowest-energy electron configuration for an atom is the one that has the maximum number of electrons with parallel spins in degenerate orbitals. (named after the German physicist Friedrich H. Hund, 1896–1997), which today says that the lowest-energy electron configuration for an atom is the one that has the maximum number of electrons with parallel spins in degenerate orbitals. By Hund’s rule, the electron configuration of carbon, which is 1s²2s²2p², is understood to correspond to the orbital diagram shown in c. Experimentally, it is found that the ground state of a neutral carbon atom does indeed contain two unpaired electrons.

When we get to nitrogen (Z = 7, with seven electrons), Hund’s rule tells us that the lowest-energy arrangement is

with three unpaired electrons. The electron configuration of nitrogen is thus 1s²2s²2p³.

At oxygen, with Z = 8 and eight electrons, we have no choice. One electron must be paired with another in one of the 2p orbitals, which gives us two unpaired electrons and a 1s²2s²2p⁴ electron configuration. Because all the 2p orbitals are degenerate, it doesn’t matter which one has the pair of electrons.

Similarly, fluorine has the electron configuration 1s²2s²2p⁵:

When we reach neon, with Z = 10, we have filled the 2p subshell, giving a 1s²2s²2p⁶ electron configuration:

Notice that for neon, as for helium, all the orbitals through the 2p level are completely filled. This fact is very important in dictating both the chemical reactivity and the bonding of helium and neon, as you will see.

Valence Electrons

As we continue through the periodic table in this way, writing the electron configurations of larger and larger atoms, it becomes tedious to keep copying the configurations of the filled inner subshells. In practice, chemists simplify the notation by using a bracketed noble gas symbol to represent the configuration of the noble gas from the preceding row because all the orbitals in a noble gas are filled. For example, [Ne] represents the 1s²2s²2p⁶ electron configuration of neon (Z = 10), so the electron configuration of sodium, with Z = 11, which is 1s²2s²2p⁶3s¹, is written as [Ne]3s¹:

Neon	Z = 10	1s22s22p6
Sodium	Z = 11	1s22s22p63s1 = [Ne]3s1

Because electrons in filled inner orbitals are closer to the nucleus and more tightly bound to it, they are rarely involved in chemical reactions. This means that the chemistry of an atom depends mostly on the electrons in its outermost shell, which are called the valence electronsElectrons in the outermost shell of an atom.. The simplified notation allows us to see the valence-electron configuration more easily. Using this notation to compare the electron configurations of sodium and lithium, we have:

Sodium	1s22s22p63s1 = [Ne]3s1
Lithium	1s22s1 = [He]2s1

It is readily apparent that both sodium and lithium have one s electron in their valence shell. We would therefore predict that sodium and lithium have very similar chemistry, which is indeed the case.

As we continue to build the eight elements of period 3, the 3s and 3p orbitals are filled, one electron at a time. This row concludes with the noble gas argon, which has the electron configuration [Ne]3s²3p⁶, corresponding to a filled valence shell.

Example 8

Draw an orbital diagram and use it to derive the electron configuration of phosphorus, Z = 15. What is its valence electron configuration?

Given: atomic number

Asked for: orbital diagram and valence electron configuration for phosphorus

Strategy:

A Locate the nearest noble gas preceding phosphorus in the periodic table. Then subtract its number of electrons from those in phosphorus to obtain the number of valence electrons in phosphorus.

B Referring to Figure 6.29 "Orbital Energy Level Diagram for a Typical Multielectron Atom", draw an orbital diagram to represent those valence orbitals. Following Hund’s rule, place the valence electrons in the available orbitals, beginning with the orbital that is lowest in energy. Write the electron configuration from your orbital diagram.

C Ignore the inner orbitals (those that correspond to the electron configuration of the nearest noble gas) and write the valence electron configuration for phosphorus.

Solution:

A Because phosphorus is in the third row of the periodic table, we know that it has a [Ne] closed shell with 10 electrons. We begin by subtracting 10 electrons from the 15 in phosphorus.

B The additional five electrons are placed in the next available orbitals, which Figure 6.29 "Orbital Energy Level Diagram for a Typical Multielectron Atom" tells us are the 3s and 3p orbitals:

Because the 3s orbital is lower in energy than the 3p orbitals, we fill it first:

Hund’s rule tells us that the remaining three electrons will occupy the degenerate 3p orbitals separately but with their spins aligned:

The electron configuration is [Ne]3s²3p³.

C We obtain the valence electron configuration by ignoring the inner orbitals, which for phosphorus means that we ignore the [Ne] closed shell. This gives a valence-electron configuration of 3s²3p³.

Exercise

Draw an orbital diagram and use it to derive the electron configuration of chlorine, Z = 17. What is its valence electron configuration?

Answer: [Ne]3s²3p⁵; 3s²3p⁵

The general order in which orbitals are filled is depicted in Figure 6.32 "Predicting the Order in Which Orbitals Are Filled in Multielectron Atoms". Subshells corresponding to each value of n are written from left to right on successive horizontal lines, where each row represents a row in the periodic table. The order in which the orbitals are filled is indicated by the diagonal lines running from the upper right to the lower left. Accordingly, the 4s orbital is filled prior to the 3d orbital because of shielding and penetration effects. Consequently, the electron configuration of potassium, which begins the fourth period, is [Ar]4s¹, and the configuration of calcium is [Ar]4s². Five 3d orbitals are filled by the next 10 elements, the transition metals, followed by three 4p orbitals. Notice that the last member of this row is the noble gas krypton (Z = 36), [Ar]4s²3d¹⁰4p⁶ = [Kr], which has filled 4s, 3d, and 4p orbitals. The fifth row of the periodic table is essentially the same as the fourth, except that the 5s, 4d, and 5p orbitals are filled sequentially.

Figure 6.32 Predicting the Order in Which Orbitals Are Filled in Multielectron Atoms

If you write the subshells for each value of the principal quantum number on successive lines, the observed order in which they are filled is indicated by a series of diagonal lines running from the upper right to the lower left.

The sixth row of the periodic table will be different from the preceding two because the 4f orbitals, which can hold 14 electrons, are filled between the 6s and the 5d orbitals. The elements that contain 4f orbitals in their valence shell are the lanthanides. When the 6p orbitals are finally filled, we have reached the next (and last known) noble gas, radon (Z = 86), [Xe]6s²4f¹⁴5d¹⁰6p⁶ = [Rn]. In the last row, the 5f orbitals are filled between the 7s and the 6d orbitals, which gives the 14 actinide elements. Because the large number of protons makes their nuclei unstable, all the actinides are radioactive.

Example 9

Write the electron configuration of mercury (Z = 80), showing all the inner orbitals.

Given: atomic number

Asked for: complete electron configuration

Strategy:

Using the orbital diagram in Figure 6.32 "Predicting the Order in Which Orbitals Are Filled in Multielectron Atoms" and the periodic table as a guide, fill the orbitals until all 80 electrons have been placed.

Solution:

By placing the electrons in orbitals following the order shown in Figure 6.32 "Predicting the Order in Which Orbitals Are Filled in Multielectron Atoms" and using the periodic table as a guide, we obtain

1s2	row 1	2 electrons
2s22p6	row 2	8 electrons
3s23p6	row 3	8 electrons
4s23d104p6	row 4	18 electrons
5s24d105p6	row 5	18 electrons
	row 1–5	54 electrons

After filling the first five rows, we still have 80 − 54 = 26 more electrons to accommodate. According to Figure 6.33 "The Periodic Table, Showing How the Elements Are Grouped According to the Kind of Subshell (", we need to fill the 6s (2 electrons), 4f (14 electrons), and 5d (10 electrons) orbitals. The result is mercury’s electron configuration:

1s²2s²2p⁶3s²3p⁶4s²3d¹⁰4p⁶5s²4d¹⁰5p⁶6s²4f¹⁴5d¹⁰ = Hg = [Xe]6s²4f¹⁴5d¹⁰

with a filled 5d subshell, a 6s²4f¹⁴5d¹⁰ valence shell configuration, and a total of 80 electrons. (You should always check to be sure that the total number of electrons equals the atomic number.)

Exercise

Although element 114 is not stable enough to occur in nature, two isotopes of element 114 were created for the first time in a nuclear reactor in 1999 by a team of Russian and American scientists. Write the complete electron configuration for element 114.

Answer: 1s²2s²2p⁶3s²3p⁶4s²3d¹⁰4p⁶5s²4d¹⁰5p⁶6s²4f¹⁴5d¹⁰6p⁶7s²5f¹⁴6d¹⁰7p²

The electron configurations of the elements are presented in Figure 6.34 "Electron Configurations of the Elements", which lists the orbitals in the order in which they are filled. In several cases, the ground state electron configurations are different from those predicted by Figure 6.32 "Predicting the Order in Which Orbitals Are Filled in Multielectron Atoms". Some of these anomalies occur as the 3d orbitals are filled. For example, the observed ground state electron configuration of chromium is [Ar]4s¹3d⁵ rather than the predicted [Ar]4s²3d⁴. Similarly, the observed electron configuration of copper is [Ar]4s¹3d¹⁰ instead of [Ar]s²3d⁹. The actual electron configuration may be rationalized in terms of an added stability associated with a half-filled (ns¹, np³, nd⁵, nf⁷) or filled (ns², np⁶, nd¹⁰, nf¹⁴) subshell. Given the small differences between higher energy levels, this added stability is enough to shift an electron from one orbital to another. In heavier elements, other more complex effects can also be important, leading to some of the additional anomalies indicated in Figure 6.34 "Electron Configurations of the Elements". For example, cerium has an electron configuration of [Xe]6s²4f¹5d¹, which is impossible to rationalize in simple terms. In most cases, however, these apparent anomalies do not have important chemical consequences.

Note the Pattern

Additional stability is associated with half-filled or filled subshells.

Blocks in the Periodic Table

As you have learned, the electron configurations of the elements explain the otherwise peculiar shape of the periodic table. Although the table was originally organized on the basis of physical and chemical similarities between the elements within groups, these similarities are ultimately attributable to orbital energy levels and the Pauli principle, which cause the individual subshells to be filled in a particular order. As a result, the periodic table can be divided into “blocks” corresponding to the type of subshell that is being filled, as illustrated in Figure 6.34 "Electron Configurations of the Elements". For example, the two columns on the left, known as the s blockThe elements in the left two columns of the periodic table in which the ns orbital is being filled., consist of elements in which the ns orbitals are being filled. The six columns on the right, elements in which the np orbitals are being filled, constitute the p blockThe elements in the six columns on the right of the periodic table in which the np orbitals are being filled.. In between are the 10 columns of the d blockThe elements in the periodic table in which the (n − 1)d orbitals are being filled., elements in which the (n − 1)d orbitals are filled. At the bottom lie the 14 columns of the f blockThe elements in the periodic table in which the (n − 2)f orbitals are being filled., elements in which the (n − 2)f orbitals are filled. Because two electrons can be accommodated per orbital, the number of columns in each block is the same as the maximum electron capacity of the subshell: 2 for ns, 6 for np, 10 for (n − 1)d, and 14 for (n − 2)f. Within each column, each element has the same valence electron configuration—for example, ns¹ (group 1) or ns²np¹ (group 13). As you will see, this is reflected in important similarities in the chemical reactivity and the bonding for the elements in each column.

Figure 6.33 The Periodic Table, Showing How the Elements Are Grouped According to the Kind of Subshell (s, p, d, f) Being Filled with Electrons in the Valence Shell of Each Element

The electron configurations of the elements are in Figure 6.34 "Electron Configurations of the Elements".

Hydrogen and helium are placed somewhat arbitrarily. Although hydrogen is not an alkali metal, its 1s¹ electron configuration suggests a similarity to lithium ([He]2s¹) and the other elements in the first column. Although helium, with a filled ns subshell, should be similar chemically to other elements with an ns² electron configuration, the closed principal shell dominates its chemistry, justifying its placement above neon on the right. In Chapter 7 "The Periodic Table and Periodic Trends", we will examine how electron configurations affect the properties and reactivity of the elements.

Figure 6.34 Electron Configurations of the Elements

The electron configurations of elements indicated in red are exceptions due to the added stability associated with half-filled and filled subshells. The electron configurations of the elements indicated in blue are also anomalous, but the reasons for the observed configurations are more complex. For elements after No, the electron configurations are tentative.