Atoms 36-1 The Atom 36-2. The Bohr Model of the Hydrogen Atom 36-3 Quantum Theory of Atoms 38-4 QuantumTheory of the Hydrogen Atom 36-5 The Spin-Orbit Effect and Fine Structure 8 The PeriodicTable 38-7 Optical Spectra and X-Ray Spectra ne hundred eleven chemical elements have been discovered, and several additional chemical elements recently have been reported but not authenti- cated, Bach element is characterized by an atom that has a: number of protons Z and an equal number of electrons. The number of protons Z.is called the atomie number. The atom that has the fewest protons is called hydrogen (H) and has Z = 1. A helium (He) atom has two protons (Z = 2), a lithium (Li) atom has thre protons (Z = 3), and so forth, Nearly all the mass of an atom is concentrated in is tiny nucleus, which is made up of protons and neutrons. {An atoms nuclear radius is approximately 1 fm to 10 fm (1 fm = 10-!m) and the radius of an atom is approximately 0.1 nm = 100,000 fim. ‘The chemical properties and physical properties of an element are determined by the number and arrangement of the electrons in an atom of the element. Because each proton has a positive charge +e, the nucleus has a total positive charge +Ze, The electrons are negatively charged (-¢,s0 they are attracted to the nucleus and repelled by each other. Because electrons and protons have equal but 1227 [AT A DISTANCE OF 6,000 LIGHTYEARS. FROM EARTH, THE STAR CLUSTER, RCW 38 5 A RELATIVELY CLOSE SSTAR-FORMING REGION. THIS IMAGE COVERS AN AREA ABOUT § LIGHTYEARS [ACROSS AND CONTAINS THOUSANDS OF HOT, VERY YOUNG STARS FORMED LESS THAN A MILLION YEARS AGO. X RAYS FROMTHE HOT UPPER [ATMOSPHERES OF 190 OF THESE ‘STARS WERE DETECTED BY CHANDRA, AN X-RAY OBSERVATORY ORBITING EARTH. THE MECHANISMS GENERATING ‘THESE X RAYS ARE NOT EARTH, X-RAY MACHINES P X RAYS BY BOMBARDING ATARGET WITH HIGH-ENERGY ELECTRONS. THE [ATOMIC NUMBER OFTHE ATOMS ‘THAT MAKE UPTHE TARGET CAN BE DETERMINED BY ANALYZINGTHE RESULTING X-RAY SPECTRA. INASACXCICHAS Wolk ta) How i the atomic number ‘obtained from the spectel analysis? (Soe Example 36-8.)1228 cHapren 36 Atoms ‘opposite changes and an atom has equal numbers of electrons and protons, atoms are electrically neutral. Atoms that lose or gain one or more electrons are then elec- trically charged and are called ions. We will begin our study of atoms by discussing the Bohr model, a semiclas- sical model developed by Niels Bohr in 1913 to explain the electromagnetic ‘spectra produced by hydrogen atoms, Although this pre-quantum mechan- Jeg model has many shortcomings, it provides a useful framework for the discussion of atomic phenomena. After discussing the Bohr model, we will then apply our knowledge of quantum mechanics from Chapter 35 to give ‘2 much more productive mode! of the hydrogen atom. We will then discuss the structure of other atoms and the periodic table of the elements. Finally, we will discuss both optical and X-ray spectra. 36-1 ATOMIC SPECTRA By the beginning of the twentieth century, a large body of data had been collected. corr the emissiorv of light by atoms inrargas-when- the atoms are-excited by anrelec tric discharge. Viewed through a spectroscope that has a narrow-slit aperture, light that has been emitted by atoms of a particular element appears as a discrete set of lines of different colors or wavelengths. The spacing and relative intensities of the lines are characteristic of the element. The wavelengths of these spectral lin could be accurately determined, and much effort went into finding regularities in the spectra. Figure 36-1 shows line spectra for hydrogen and for mercury. In 1885, Johann Balmer determined that the wavelengths of the lines in the vi ible spectrum of hydrogen can be represented by the formula a m=3,4,5, 36-1 (364.6 nm) 4 Balmer suggested that this expression might be a special case of a more general expression that would be applicable to the spectra of other elements, Such an expres- sion, found by Johannes R. Rydberg and Walter Ritz and known as the Rydberg- Ritz formula, gives the reciprocal wavelength as (Goan (aot rom Easter Kodak ad Wabash Instrument Corporation)‘The Bohr Model of the Hydrogen Atom SECTION 30-2 1228 where 1, and mt, are integers, 1, > my and R is the Rydberg constant. The Rydberg, constant does vary slightly, and in a regular way, from element to element, For hy- drogen, has the value Ry = 1.097776 x 10? m™ RYDBERG CONSTANT FOR HYDROGEN ‘The Rydberg-Ritz formula gives the wavelengths for all the lines in the spectra of hydrogen, as well as alkali elements such as lithium and sodium. The hy- ‘drogen Balmer series given by Equation 36-1 is also given by Equation 36-2, with R= Ry 1, = 2, and 1, =m. Many attempts were made to construct a model of the atom that would yield these formulas for an atoms radiation spectrum. The most popular model, created by] J. Thomson, considered various arrangements of electrons embedded in some kind of fluid that had most of the mass ofthe atom and had enough positive charge to make the atom electrically neutral. Thomson's model, called the “plum pud- ding” model, is illustrated in Figure 36-2. Because classical electromagnetic theory predicted that a charge oscillating with frequency f wotld radiate electromagnetic energy of that frequency, Thomson searched for configurations that were stable land that had normal modes of vibration of frequencies equal to those of the spec- trum of the atom. A difficulty of this model and all other models was that, accord- ing to classical physics, electric forces alone cannot produce stable equilibrium. ‘Thomson was unsuccessful in finding a model that predicted the observed fre- quencies for any atom. “The Thomson model was essentially ruled out by a set of experiments by H. W. Geiger and E. Marsden, under the supervision of E. Retherford in approximately 1911, in which alpha particles from radioactive radium were scattered by atoms in a gold foil Rutherford showed that the number of alphe particles scattered at large Angles could not be accounted for by an atom in which the positive charge was dis- tributed throughout the atom (known to be about 0.1 nm in diameter). Instead, the results suggested thatthe positive charge and most ofthe mass of an atom is con- centrated in a very small region, now called the nuclevs, which has a diameter of the order of 10-* nm = 1 fm. Ki” THE BOHR MODEL OF THE Pec Niels Bohr, working in the Rutherford laboratory in 1912, proposed a model of the hydrogen atom that extended the work of Planck, Einstein, and Rutherford and successfully predicted the observed spectra. According to Bohr’s model, the electron of the hydrogen atom moves in either a circular or an elliptical orbit around the positive nucleus according to Coulomb's law and classical mechanics like the planets orbit the Sun. For simplicity, Bohr chose a circular orbit, as shown, in Figure 36-3. ENERGY FOR A CIRCULAR ORBIT Consider an electron of charge ~¢ moving in a circular orbit of radius r about a pos- itive charge +Ze such as the nucleus of a hydrogen atom (Z = 1) or of a singly ionized helium atom (Z. = 2). The total energy of the electron can be related to the Fioune 36-2 J.J. Thomson's plum pudding model of the atom. in this model the lectrons, which have a negative charge, are embedded ina fd of postive charge. Fora given configuration in such a system, the resonance frequencies of osllations ofthe tlectrons can be calculated. According to Classical theory, the atom should radiate light fof frequency equal the frequency of ‘oscillation ofthe electrons. Thomson could not find any configuration that would give frequencies in agreement with the measured frequencies ofthe spectrum of any atom. FIGURE 36-3 Electron of charge ~ traveling ina ciculae orbit of radius r around the nuclear charge +Ze. The attractive electrical force KZ? keops the electron in its obit1230 | HAPTER 36 Atoms radius of the orbit. The potential energy of the electron of charge ~e at a distance r from a positive charge Ze is Hite _ Hz u 36-3 where kis the Coulomb constant. The kinetic energy K can be obtained as a fune- tion of r by using Newton’s second law, F,., = ma. Setting the Coulomb attractive ee = 36-40 ‘Multiplying both sides by r/2 gives 1g Laz = jm 36-40 ‘Thus, the kinetic energy and the potential energy vary inversely with r. Note that the magnitude of the potential energy is twice that of the kinetic energy: U = -2K 365 Equation 36-5 a general result for particles orbiting under the influence of forces that vary inversely with the square of the distance from a fixed point. [It also holds for circular orbits in a gravitational field (see Example 11-6 in Section 11-3). ‘The total energy is the sum of the kinetic energy and the potential energy: 1kze ki Enis ainh 2 Paes 36-6 ENERGY IN A CIRCULAR ORBIT FOR A 1/7? FORCE Although mechanical stability is achieved because the Coulomb attractive force provides the centripetal force necessary for the electron to remain in orbit, classical electromagnetic theory says that such an atom would be electrically unstable. The atom would be unstable because the electron must accelerate when moving in a circle and therefore radiate electromagnetic energy of frequency equal to that of its, motion. According to the classical theory, such an atom would quickly collapse as, the electron spiraled into the nucleus and radiated away the energy. BOHR’S POSTULATES Bohr circumvented the difficulty of the collapsing atom by postulating that only certain orbits, called stationary states, are allowed and that an atom with an elec- tron in one of these orbits does not radiate. An atom radiates only when the elec- tron makes a transition from one allowed orbit (stationary state) to another. ‘The electron in the hydrogen atom can move only in certain nonradiating, circular orbits called stationary states. BOHA'S FIRST POSTULATE—NONRADIATING ORBITS. Bohr's second postulate relates the frequency of radiation to the energies of the stationary states. If E, and E, are the initial and final energies of the atom, the fre- quency of the emitted radiation during a transition is given by 36-7 BOHR'S SECOND POSTULATE—PHOTON FREQUENCY FROM ENERGY CONSERVATIONcrate Fr) Leb ales Ted ee the squares of integers. Bohr searched for a quantum condition for the radii of the stable orbits that would yield this result. After much trial and error, Bohr found that he could obtain the desired result if he postulated that the magnitude of the angular momentum of the electron in a stable orbit equals an integer multiplied by fi. Because the magnitude of the angular momentum of a circular orbit is just ro, this postulate is Litre ret rte rhea tei yo mor,= nh n= 1,2,3, 369 BOHR’S THIRD POSTULATE—QUANTIZED ANGULAR MOMENTUM where fi = h/2m = 1.055 x 10°3'J-s = 6.582 x 107% eVs. Equation 36-9 relates the speed 0, to the radius 1, of the orbit that has angular momentum ri, Equation 36-4a gives us another equation relating the speed to the radius 36-10 We can determine r, by first solving for v, in Equation 36-9. Squaring the result then gives gent 1uating this expression for 02 with the expression given by Equation 36-10, we get 8 % p y 8 pte _ ke "ee mr, Solving for r,, we obtain ee 36-11 RADII OF THE BOHR ORBITS where is called the first Bohr radius. According to the Bohr model , is the or- bital radius of the electron in a hydrogen atom that has 1 = 1 REO e 1529 nm. 12 inet ~ met ~ 909° oe FIRST BOHR RADIUSa amccccccaaaaacaaaaaaaias saz | CHAPTER 20, Atoms ‘Substituting the expressions for r, in Equation 36-11 into Equation 36-8 for the fre~ quency gives 11). pmb _ G-)--SG-3 If we compare this expression where Z= 1 and f = c/A with the empirical Rydberg Ritz formula (Equation 36-2), we obtain for the Rydberg constant met met “neh” Bech? Using the values of m, ek, and f known in 1913, Bohr calculated R and found his result to agree (within the limits ofthe uncertainties of the constants) with the ‘value obtained from spectroscopy. 36-14 ‘Standing-Wave Condition Implies Quantization of Angular Momentum For waves in a circle, the standing-wave condition is that there is an integral number of [wavelengths in the circumference. That is. "A, = 2a, where t= 1,2,3, and so on. Show that this condition for electron waves implies quantization of angular momentum. PICTURE ‘The wavelength and the momentum are elated by the de Broglie relation p = Wi/A (Equation 3413). Using this relation and the standing wave condition "A, = 2rr, to relate the momentum to the radius. sowe 1 Wit he sting condton mom, 2 ete derglton atin 41) tretette p= = ‘momentum p to Ay Ty 2. Sovefrry Teanguarmonetumotanccenina p= [ET circular orbit is mor, = pry, where p = mo: [enter sep oui ck ish te prem stent ash us show ENERGY LEVELS “The total mechanical energy of the electron in the hydrogen atom is related to the radius ofthe circular orbit by Equation 36-6. If we substitute the quantized values of ras given by Equation 36-11, we obtain 1 mize 2 he or 3615 ENERGY LEVELS IN THE HYDROGEN ATOM where 36-16The Bohr Model of the Hydrogen Atom SECTION 36-2 1233 ‘The energies E, corresponding to Z = 1 are the quantized allowed energies for the " Eyev hydrogen atom, rn ‘Transitions between these allowed energies result in the emission or absorption ‘of a photon whose frequency is given by f = (E, ~ E)/h,and whose wavelength is st ek anGraeE 3617 “340 As we found in Chapter 34, itis convenient to have the value of hc in electron-volt nanometers: he = 1240 eVenm, 36-18 Because the energies are quantized, the frequencies and wavelengths of the radi tion emitted by the hydrogen atom are quantized in agreement with the observed line spectrum. Figure 36-4 shows the energy-level diagram for hydrogen. The energy of the hydrogen atom in the ground state is E, = ~13.6 eV. Asm approaches infinity the ‘energy approaches zero. The process of removing an electron from an atom is, called ionization, and the minimum amount of energy required to remove the electron is the ionization energy. The ionization energy of the ground-state hy- drogen atom, which is also its binding energy, is 13.6 eV. A few transitions from a higher state to a lower state are indicated in Figure 36-4. When Bohr published his model of the hydrogen atom, the Balmer series (corresponding to n, = 2 and n,=3,4,5, ...) and the Paschen series (corresponding to ™=3 and Lyman series 1m, = 4,5,6, ...) were known. In 1916, T. Lyman found the series corresponding to | i, = 1.F Brackett in 1922 and H. A. Pfund in 1924 found the series corresponding FIGURE 36-4 Enengy-level diagram for ton, = 4and n, = 5, respectively: Only the Balmer series lies in the visible portion hydrogen showing the frst few transitions in of magnetic spectrum. each of the Lyman, Balmer, and Paschen HTT RMT series. The energies ofthe levels are given by Equation 3615. qT Do not think the A in Equation 36-17 is the wavelength of the A136 Longest Wavelength in the Lyman Series Find (a) the energy and (b) the wavelength ofthe spectral line that length in the Lyman series. he longest wave- electron, It is not. It is the wavelength of the emitted or absorbed photon, PICTURE Forthe Lyman series n, = 1, rom Figure 364, we can see that the Lyman series corresponds to transitions ending atthe ground state energy, E,~ E, = ~13.6 eV. Because the photon wavelength A varies inversely with energy, the transition that has the longest ‘wavelength isthe transition that has the lowest energy, which i from the first excited state i = 2 to the ground state m = 1 SOwvE 1. The energy of the photon is the difference inthe energies of the intial and final atomic states: “néev P = -34vev + 136ev = [1020] 1240eV-nm 102eV Tznm| 2. The wavelength of the photon is A CHECK The step-1 result of 102 eV is less than 13.6 eV (the binding energy of ground-state hydrogen), This result is expected. ‘TAKING IT FURTHER ‘This photon has a wavelength that corresponds tothe ultraviolet region. ofthe electromagnetic spectrum, Because all the other lines in the “yman series have even greater energies and shorter wavelengths, the Lyman series is completly inthe ultraviolet region, PRACTICE PROBLEM 36-1 Find the shortest wavelength fora lin in the Lyman series.124 | CHAPTER 36 Atoms Despite its spectacular successes, the Bohr model of the hydrogen atom had many shortcomings. There was no justification for the postulates of stationary states or for the quantization of angular momentum other than the fact that these postulates led to energy levels that agreed with spectroscopic data. Furthermore, attempts to apply the model to atoms that have more electrons and protons had lit- tle success. The quantum-mechanical model resolves these difficulties. The sta- tionary states of the Bohr model are replaced by the standing- wave solutions of the Schrddinger equation analogous to the standing electron waves for a particle in a box discussed in Chapter 34 and Chapter 35. Energy quantization is a direct con- sequence of the standing-wave solutions of the Schrédinger equation. For hydro- gen, these quantized energies agree with those obtained from the Bohr model and with experiment. The quantization of angular momentum that had to be postu- lated in the Bohr model is predicted by the quantum theory. Ries QUANT THEORY OF ATOMS THE SCHRODINGER EQUATION IN SPHERICAL COORDINATES In quantum theory, an electron in an atom is described by its wave function y. The probability of finding the electron in some volume dV of space equals the square of the absolute value of the wave function |p|? multiplied by dV. Boundary condi- tions on the wave function lead to the quantization of the wavelengths and fre- quencies and thereby to the quantization of the electron energy. Consider a single electron of mass m moving in three dimensions in a region in. hich the potential energy is U. The time-independent Schrdinger equation for such a particle is given by Equation 35-30: K ( PH Ow ax ay?” a2", suave =e a6 Fora single isolated atom, the potential energy UI depends only on the radial dis- tance r= V2? + y? + 2 of the electron from the center of the nucleus. The prob- Jem is then most conveniently treated using the spherical coordinates r,0, and 6, ‘which are related to the rectangular coordinates x,y, and z by z= rcos8 x= rsinO cos 36-20 ya rsind sing ‘These relations are shown in Figure 36-5, The transformation of Equation, 36-19 from rectangular to spherical coordinates is a straightforward, but tedious, calculation, which we will omit. The result of this transformation can be found in Problem 42. We will discuss qualitatively some of the in- teresting features of the wave functions that satisfy this equation. The transformed version of Equation 36-19 can be solved using the technique called separation of variables, This is accomplished by express- ing the wave function W(r, 6, @) as a product of three functions, each of Which i a function of only one of the three spherical coordinates W.8.8) = ROFOS@) 3621 ‘where R is a function that depends only on the radial coordinate r,f is a function that depends only on the polar coordinate 0, and g is a function that depends only on the azimuth coordinate ¢. When this form of Wr, 8,6) is substituted into the Schrbdinger equation, the Schrddinger equation can be transformed into three ordinary differential equations, one for R(7), one for f(@), and one for g(¢). The potential energy U(r) ap- pears only in the equation for R(7), which is called the radial equation. FIGURE 36-8 Geometric relations between spherical coordinates and rectangular coordinates.