CHAPTER Atoms

37

1* As n increases, does the spacing of adjacent energy levels increase or decrease? The spacing decreases. 2 The energy of the ground state of doubly ionized lithium (Z = 3) is ______ ,where E0 = 13.6 eV. (a ) 9E0, (b ) 3E0, (c) E0/3, (d ) E0/9. (a ) 3 Bohrs quantum condition on electron orbits requires _ (a ) that the angular momentum of the electron about the hydrogen nucleus equal nh . (b ) that no more than one electron occupy a given stationary state. (c) that the electrons spiral into the nucleus while radiating electromagnetic waves. (d ) that the energies of an electron in a hydrogen atom be equal to nE0, where E 0 is a constant energy and n is an integer. (e) none of the above. (a ) 4 If an electron moves to a larger orbit, does its total energy increase or decrease? Does its kinetic energy increase or decrease? Its total energy increases; its kinetic energy decreases. 5* The kinetic energy of the electron in the ground state of hydrogen is 13.6 eV = E0. The kinetic energy of the electron in the state n = 2 is _____. (a ) 4E0, (b ) 2E0, (c) E0/2, (d ) E0/4. (d ) 6 The radius of the n = 1 orbit in the hydrogen atom is a 0 = 0.053 nm. What is the radius of the n = 5 orbit? (a ) 5a 0, (b ) 25a 0, (c) a 0, (d ) (1/5) a 0, (e) (1/25) a 0. (b ) 7 Use the known values of the constants in Equation 37-11 to show that a 0 is approximately 0.0529 nm. _ Evaluate Equ. 37-12, a 0 = h 2/mke2
(1.05 10 34 )2 9.11 10 31 8.99 109 (1.6 10 19 )2 m

a0 =

= 5.261011 m = 0.0526 nm

The longest wavelength of the Lyman series was calculated in Example 37-2. Find the wavelengths for the transitions (a ) n 1 = 3 to n 2 = 1 and (b ) n 1 = 4 to n 2 = 1.

Chapter 37

Atoms

? = (1240/?E) nm, where ?E = Ei Ef and the energies are in eV (see Equs. 17-5 and 17-21); here Ef = -13.6 eV. (a ) E3 = 13.6/9 eV = 1.51 eV (b ) E4 = 13.6/16 eV = 0.85 eV ?E = 12.09 eV; ? = 102.6 nm ?E = 12.75 eV; ? = 97.25 nm

9* Find the photon energy for the three longest wavelengths in the Balmer series and calculate the wavelengths. For the Balmer series, Ef = E(n = 2) = 3.40 eV. Use Equs. 17-5 and 17-21, i.e., ? = (1240 eV.nm)/(?E eV). ?E = 1.89 eV; ?3,2 = 656.1 nm 1. ?E = E3 E2; E3 = 13.6/9 eV = 1.51 eV ?E = 2.55 eV; ?4,2 = 486.3 nm 2. ?E = E4 E2; E4 = 13.6/16 eV = 0.85 eV ?E = 2.856 eV; ?5,2 = 434.2 nm 3. ?E = E5 E2; E5 = 13.6/25 eV = 0.544 eV 10 (a ) Find the photon energy and wavelength for the series limit (shortest wavelength) in the Paschen series (n 2 = 3). (b ) Calculate the wavelengths for the three longest wavelengths in this series and indicate their positions on a horizontal linear scale. _ (a ) For ?min, n = and Ei = 0 h f = (13.6/9) eV = 1.51 eV; ?min = 1240/1.51 nm = 820.6 nm (b ) For the three longest ?, n i = 4, 5, and 6 ?E4,3 = 0.66 eV; ?4,3 = 1876 nm ?E5,3 = 0.967 eV; ?5,3 = 1282 nm ?E6,3 = 1.133 eV; ?6,3 = 1094 nm The positions of these lines on a horizontal linear scale are shown below with the wavelengths indicated.

11 Repeat Problem 10 for the Brackett series (n 2 = 4). _ (a ) For ?min, n = and Ei = 0 h f = (13.6/16) eV = 0.85 eV; ?min = (1240/0.85) nm = 1459 nm ?E5,4 = 0.306 eV; ?4,3 = 4052 nm ?E6,4 = 0.472 eV; ?5,3 = 2627 nm ?E7,4 = 0.572 eV; ?6,3 = 2166 nm The positions of these lines on a horizontal linear scale are shown below with the wavelengths indicated. (b ) For the three longest ?, n i = 5, 6, and 7

Chapter 37

Atoms

12 A hydrogen atom is in its tenth excited state according to the Bohr model (n = 11). (a ) What is the radius of the Bohr orbit? (b ) What is the angular momentum of the electron? (c) What is the electrons kinetic energy? (d ) What is the electrons potential energy? (e) What is the electrons total energy? (a ) Use Equs. 37-11 and 37-12 r11 = 121a 0 = 6.40 nm _ L = 111.051034 J.s = 11.61034 J.s (b ) L = nh K = 13.6/121 eV = 0.112 eV (c) K = E0/n 2 U = 0.225 eV (d ) U = 2K 2 E = 0.112 eV (e) E = E0/n 13* The binding energy of an electron is the minimum energy required to remove the electron from its ground state to a large distance from the nucleus. (a ) What is the binding energy for the hydrogen atom? (b ) What is the binding energy for He+? (c) What is the binding energy for Li2+? [Singly ionized helium (He+) and doubly ionized lithium (Li2+) are hydrogen-like in that the system consists of a positively charged nucleus and a single bound electron.] (a ) BE = E E(n = 1) = E0 BE = 13.6 eV 2 + (b ) Note that En Z ; Z for He = 2 BE = 413.6 eV = 54.4 eV 2+ (c) For Li , Z = 3 BE = 913.6 eV = 122.4 eV 14 The electron of a hydrogen atom is in the n = 2 state. The electron makes a transition to the ground state. (a ) What is the energy of the photon according to the Bohr model? (b ) The linear momentum of the emitted photon is related to its energy by p = E/c. If we assume conservation of linear momentum, what is the recoil velocity of the atom? (c) Find the recoil kinetic energy of the atom in electron volts. By what percentage must the energy of the photon calculated in part (a ) be corrected to account for this recoil energy? (a ) hf = E2 E1 = 3E0/4 hf = 10.2 eV = 1.6321018 J (b ) hf /c = p rec; vrec = p rec/m = hf /mc vrec = 1.6321018/(1.671027 3108 ) m/s = 3.26 m/s (c) Erec = p rec2/2m = (hf )2/2mc2 Erec = (10.2) 2/(2938.3106 ) eV = 5.54108 eV Percent correction = 5.54106/10.2 = 5.44107% 15 Show that the speed of an electron in the n th Bohr orbit of hydrogen is given by vn = e2/2e0hn . _ _ _ Ln = nh = mvnrn = n 2h 2mvn/mke2; solving for vnwe obtain vn = ke2/nh . But k =1/4pe0, so vn = e2/2e0hn .

16 In this problem you will estimate the radius and the energy of the lowest stationary state of the hydrogen atom using the uncertainty principle. The total energy of the electron of momentum p and mass m a distance r from the proton in the hydrogen atom is given by E = p 2/2m ke 2/r, where k is the Coulomb constant. Assume that the minimum value of p 2 is p 2 (?p )2 = h 2/r2, where ?p is the uncertainty in p and we have taken ?r ~ r for the order of magnitude of the uncertainty in position; the energy is E = h 2/2mr2 ke2/r. Find the radius rm for which this energy is a minimum, and calculate the minimum value of E in electron volts. With E = h 2/2mr2 ke2/r, dE/dr = ke2/r2 - h 2/mr3. Set dE/dr = 0 and solve for r = rm; rm = h 2/ke2m. This is just the Bohr radius a 0. Consequently, the energy is the ground state energy of the hydrogen atom, namely ,13.6 eV. 17* In a reference frame with the origin at the center of mass of an electron and the nucleus of an atom, the

Chapter 37

Atoms

electron and nucleus have equal and opposite momenta of magnitude p. (a ) Show that the total kinetic energy of the electron and nucleus can be written K = p 2/2mr, where mr = meM /(M + me) is called the reduced mass, me is the mass of the electron, and M is the mass of the nucleus. It can be shown that the motion of the nucleus can be accounted for by replacing the mass of the electron by the reduced mass. In general, the reduced mass for a two-body problem with masses m1 and m2 is given by
mr = m1 m2 m1+ m 2

(Eq. 37-47)

(b ) Use Equation 37-14 with m replaced by mr to calculate the Rydberg constant for hydrogen (M = mp) and for a very massive nucleus (M = ). (c) Find the percentage correction for the ground-state energy of the hydrogen atom due to the motion of the proton. (a ) Both the electron and nucleus have the same momentum, so K = Ke + Kn = p 2/2me + p 2/2M = (p 2/2)[(me + M /meM )]. Defining mr = meM /(me + M ), K = p 2/2mr. _ (b ) For H, RH = 1.096776107 m1 = Cmr, where C = k 2e4/4pch 3, and mr = mpme/(me + mp) = me/(1 + me/mp) = me/(1 + 5.447104). If instead of mp we have an infinite nuclear mass, then mr = me, and the Rydberg constant R is then greater than RH by the factor (1 + 5.447104), or R = 1.097373107 m1. (c) The energy correction is just 5.447104 or 0.0545%. That is, the correct energy is slightly less than that calculated neglecting the motion of the nucleus. 18 For the principal quantum number n = 4, how many different values can the orbital quantum number l have? (a ) 4, (b ) 3, (c) 7, (d ) 16, (e) 6. (b ) 19 For the principal quantum number n = 4, how many different values can the magnetic quantum number m have? (a ) 4, (b ) 3, (c) 7, (d ) 16, (e) 6. (c ) 20 For l = 1, find (a ) the magnitude of the angular momentum L and (b ) the possible values of m. (c) Draw to scale a vector diagram showing the possible orientations of L with the z axis. (a ) Use Equ. 37-24 (b ) m = l ...0...+ l (c) The vector diagram is shown on the right. Note that since Lz = _ _ mh and L = 2 h , the vectors for m = 1 and m = 1 must make angles of 45 with the z axis. L= _ 34 m2 =h 1, = 0, 1.49 +1 10 J.s

Chapter 37

Atoms

21*

Work Problem 20 for l = 3. _ L=2 3h m = 3, 2, 1, 0, +1, +2, +3

(a ) Use Equ. 37-24 (b ) m = l ... 0 ...+ l (c) The vector diagram is shown on the right. Note that since Lz = mh

_ and L = 2 3 h

, the angles between the vectors and the z axis are given by cos ?m = m/2 3 . Thus, ? 3 = 30, ? 2 = 54.7, and ? 1 = 73.2. As shown, the spacing between the allowed _ values of Lz is constant and equal to h . 22 A compact disk has a moment of inertia of about 2.3105 kgm2. (a ) Find its angular momentum L when it is rotating at 500 rev/min. (b ) Find the approximate value of the quantum number l for this angular momentum. 3 (a ) L = I? ? = (2p500/60) rad/s; L = 1.2010 J.s _ l 1.20103/1.0551034 1031 (b ) l L/h 23 If n = 3, (a ) what are the possible values of l ? (b ) For each value of l in (a ), list the possible values of m. (c) Using the fact that there are two quantum states for each value of l and m because of electron spin, find the total number of electron states with n = 3. l = 0: m = 0; l =1: m = 1, 0, 1; l = 2: m = 2, 1, (a ), (b ) See Equ. 37-23 0, 1, 2 (c) We will first derive the number of electron states for an arbitrary value of n and then substitute the specific
n 1

value of n . The number of m states for a given n is given by N m

l =0

n 1

(2l + 1) = 2

l=0

n 1

l+

l =0

(1).

The sum of all integers from 0 to p is p (p + 1)/2, so the first term is 2[(n 1)n /2] = n 2 n . The second term is just equal to n . So Nm = n 2. Since N, the number of electron states is twice the number of m states, the number of electron states is N = 2n 2. For n = 3, N = 18.

Chapter 37

Atoms

24 Find the total number of electron states with (a ) n = 2 and (b ) n = 4. (See Problem 23.) (a ), (b ) Use the result of Problem 23( c) (a ) N = 8; (b ) N = 32 25 * Find the minimum value of the angle ? between L and the z axis for (a ) l = 1, (b ) l = 4, and (c) l = 50. We consider the general case. The minimum angle between the z axis and L is the angle between the L vector _ _ _ for m = l and the z axis. In this case, Lz = mh = l h and L = l ( l + 1) h . Consequently, cos ? = l /( l + 1) . (a ) For l = 1, cos ? = 1/ 2 (b ) For l = 4, cos ? = 2/ 5 (c) For l = 50, cos ? =
50/51

? = 45 ? = 26.6 ? = 8.05

26 What are the possible values of n and m if (a ) l = 3, (b ) l = 4, and (c) l = 0? (a ), (b ), (c) See Equ. 37-23 (a ) n 4, m = 3, 2, 1, 0, 1, 2, 3 (b ) n 5, m = 4, 3, 2, 1, 0, 1, 2, 3, 4 (c) n 1, m = 0 27 What are the possible values of n and l if (a ) m = 0, (b ) m = -1, and (c) m = 2? (a ), (b ), (c) See Equ. 37-23 (a ) n 1, l 0; (b ) n 2, l 1; (c) n 3, l 2 28 For the ground state of the hydrogen atom, find the values of (a ) ?, (b ) ? 2, and (c) the radial probability density P(r) at r = a 0. Give your answers in terms of a 0. (a ) Use Equ. 37-33 with Z = 1 ?(a 0) = 1/(ea0 a 0 ) 2 2 3 (b ) Take the square of ?(a 0) ? (a 0) = 1/(e pa 0 ) (c) Use Equ. 37-34 and result of (b ) P(a 0) = 4/a 0e2 29* (a ) If spin is not included, how many different wave functions are there corresponding to the first excited energy level n = 2 for hydrogen? (b ) List these functions by giving the quantum numbers for each state. (a ), (b ) For n = 2, l = 0 or 1; for l = 1, there are There are four functions; they are listed by (n , l , m): three values of m, namely m = 1, 0, 1 (2,0,0), (2,1,1), (2,1,0), (2,1,1) 30 For the ground state of the hydrogen atom, find the probability of finding the electron in the range ?r = 0.03a 0 at (a ) r = a 0 and (b ) r = 2a 0. (a ) 1. Write P(a 0), see Problem 28 P(a 0) = 4/a 0e2 2. For ?r << a 0, neglect change in P(r) Probability = P(r) dr = 40.03/e2 = 0.0162 (b ) Find P(2a 0); use Equ. 37-33; proceed as in (a ) P(2a 0) = 16/a 0e4; Probability = 0.00879 31 The value of the constant C2,0,0 in Equation 37-36 is
C 2,0,0 1 = 4 2 Z a0
3/2

Find the values of (a ) ?, (b ) ? 2, and (c) the radial probability density P(r) at r = a 0 for the state n = 2, l = 0,

Chapter 37 m = 0 in hydrogen. Give your answers in terms of a 0. (a ) 1. Use Equ. 37-36 and C2,0,0 as given; Z = 1 2. Set r = a 0 and evaluate (b ) Square the result of (a ) (c) P(r) = 4pr2?2(r), Equ. 37-34

Atoms

1 r r/2a0 2,0,0 = . 2 e 4 4 a0 a0 3/2 ?2,0,0(a 0) = 0.0605/a 0 (?2,0,0(a 0))2 = 0.00366/a 03 P(a 0) = 0.046/a 0 1

3/2

32 Show that the radial probability density for the n = 2, l = 1, m = 0 state of a one-electron atom can be written 2 4 Zr/ as P(r) = A cos r e a0 , where A is a constant. The wave function for the state (2,1,0), ?2,1,0, is given by Equ. 37-37, and the probability density by Equ. 37-34. 2 2 2 2 Zr/ a 0 2 = A r 4 cos 2 ? e Zr/ a 0 , where A = 4 p C 2 Thus, P(r) = 4p r 2 C 2 2 ,1 ,0 (Z/ a 0 ) r cos ? e 2 ,1,0 Z / a 0 . 33* Calculate the probability of finding the electron in the range ?r = 0.02a 0 at (a ) r = a 0 and (b ) r = 2a 0 for the state n = 2, l = 0, m = 0 in hydrogen. (See Problem 31 for the value of C2,0,0.) In this instance, P(r) dr extends over a sufficiently narrow interval ?r << a 0 that one may neglect the dependence of P(r) on r, i.e., we will set P(r) dr = P(r) ?r. 3/2 (a ) 1. Use Equ. 37-36 and C2,0,0 as given; Z = 1 1 1 r r/2a0 2,0,0 = 2 e 4 4 a0 a0 3/2 ?2,0,0(a 0) = 0.0605/a 0 2. Set r = a 0 and evaluate (?2,0,0(a 0))2 = 0.00366/a 03 3. Square the result of (1) P(a 0) = 0.046/a 0 4. P(r) = 4pr2?2(r), Equ. 37-34 Probability = 0.0460.02 = 9.2104 5. Probability = P(a 0)?r (b) Use (a ) part 1; find ?2,0,0(2a 0) and P(2a 0) P(a 0) = 0; Probability = 0

34 The radial probability distribution function for a one-electron atom in its ground state can be written P(r) = C r2 e 2Zr/ a0 , where C is a constant. Show that P(r) has its maximum value at r = a 0/Z. To determine where P(r) is a maximum, differentiate with respect to r and set the derivative equal to 0. dP = C[2 r e2Zr/ a0 (2 Z r 2 / a 0 ) e2Zr/ a0 ] = (2 C Z r/ a0 ) e2Zr/ a0 ( a 0 /Z r) . This is zero when r = a 0/Z. dr 35 Find the expectation value of r, r = 0 rP(r) dr for hydrogen in its ground state.

< r >= 4r
0

12, 0, 0 dr
n +1

. We substitute Equ. 37-33 for ?1,0,0: < r >= 4 /

a3 0

) r e
0

3 2r / a0

dr . The integral

x
0

ax

dx = n! / a

, so

00

4 e 2r / a0 dr = 3a 0 / 8. Thus, r = 3a 0/2.

36 Show that the number of states in the hydrogen atom for a given n is 2n 2.
n 1

The number of m states for a given n is given by N m =

l =0

n 1 l=0

(2l + 1) = 2

l+

l =0

(1). The sum of all

n 1

Chapter 37

Atoms

integers from 0 to p is p (p + 1)/2, so the first term is 2[(n 1)n /2] = n 2 n . The second term is just equal to n . So Nm = n 2. Since N, the number of electron states, is twice the number of m states, the number of electron states is N = 2n 2. 37* Calculate the probability that the electron in the ground state of a hydrogen atom is in the region 0 < r < a 0.
a0

We evaluate

4r
0

a0 2

12,0, 0 (r )dr
2 bx

3 (4 / a 0 )

r
0

2 2r / a0

(2r

2 / a0 + 2r / a 0 + 1

a0 0

= 1 5e 2 = 0 .323 ,

where we have used x e dx = ( e / b3 )( b 2 x2 2bx + 2) .

38 The potential energy of a magnetic moment in an external magnetic field is given by U = uB. (a ) Calculate the difference in energy between the two possible orientations of an electron in a magnetic field B = 0.600 T k . (b ) If these electrons are bombarded with photons of energy equal to this energy difference, spin flip transitions can be induced. Find the wavelength of the photons needed for such transitions. This phenomenon is called electron spin resonance. (a ) Use Equ. 37-5; B = 5.79105 eV/T ?E = 25.791050.600 eV = 6.95105 eV 5 7 (b ) ? = hc/?E ? = (1240/6.9510 ) nm = 1.7810 nm = 1.78 cm 39 The total angular momentum of a hydrogen atom in a certain excited state has the quantum number j = 1/2. What can you say about the orbital angular-momentum quantum number l ? l = j 1, l = 0 or 1 j = l 1/2 40 The total angular momentum of a hydrogen atom in a certain excited state has the quantum number j = 11/2. What can you say about the orbital angular-momentum quantum number l ? l = j 1, l = 1 or 2 j = l 1/2 41* A hydrogen atom is in the state n = 3, l = 2 . (a ) What are the possible values of j ? J = l 1/2 j = 3/2 or 5/2 42 The p state of an electronic configuration corresponds to (a ) n = 2, (b ) l = 2, (c) l = 1, (d ) n = 0, (e) l = 0. (c ) 43 Why is the energy of the 3s state considerably lower than that of the 3p state for sodium, whereas in hydrogen these states have essentially the same energy? The s state, with l = 0, is a penetrating state in which the probability density near the nucleus is significant. Consequently, the 3s electron in sodium is in a region of low potential energy for a significant portion of the time. In the state l = 1, the probability density at the nucleus is zero, so the 2p electron of sodium is shielded from the nuclear charge by the 1s electrons. In hydrogen, the 3s and 2p electrons experience the same nuclear potential. 44 Discuss the evidence from the periodic table of the need for a fourth quantum number. How would the properties of He differ if there were only three quantum numbers, n , l , and m? In conformity with the exclusion principle, the total number of electrons that can be accommodated in states of quantum number n is n 2 (see Problem 36). The fact that closed shells correspond to 2n 2 electrons indicates that there is another quantum number that can have two possible values.

Chapter 37

Atoms

45* The properties of iron (Z = 26) and cobalt (Z = 27), which have adjacent atomic numbers, are similar, whereas the properties of neon (Z = 10) and sodium (Z = 11), which also have adjacent atomic numbers, are very different. Explain why. For iron and cobalt, the closed shell configuration is the same; the only difference is the number of 3d electrons. Neon is a closed shell configuration (n = 1, 2), whereas sodium has one extra electron outside a closed shell. The properties of neon are therefore similar to those of helium and other rare gas atoms, whereas those of sodium are similar to those of hydrogen and other atoms (lithium, potassium) with one electron outside a closed shell. 46 Separate the following six elementspotassium, calcium, titanium, chromium, manganese, and copperinto two groups of three each such that those in a group have similar properties. Titanium, manganese, and calcium all have an outer 4s 2 configuration in the ground state. Potassium, chromium, and copper all have an outer 4s configuration in the ground state. It is to be expected that atoms of the first group will have similar properties, and, likewise, that atoms of the second group will have similar properties. 47 What element has the electron configuration (a ) 1s 22s22p63s23p2 and (b ) 1s 22s22p63s23p64s2? (a ) Here Z = 14. The element is silicon. (b ) Here Z = 20. The element is calcium. 48 The total number of quantum states of hydrogen with quantum number n = 4 is _____. (a ) 4, (b ) 16, (c) 32, (d ) 36. (c ) 49* How many of oxygen's eight electrons are found in the p state? (a ) 0, (b ) 2, (c) 4, (d ) 6, (e) 8. (c ) 50 Write the electron configuration of (a ) carbon and (b ) oxygen. (a ) Carbon: 1s 22s22p2. (b ) Oxygen: 1s 22s22p4. 51 Write the electron configuration of (a ) aluminum and (b ) chromium. (a ) Aluminum: 1s22s22p63s23p. (b ) Chromium: 1s 22s22p63s23p63d 34s. 52 Give the possible values of the z component of the orbital angular momentum of (a ) a d electron and (b ) an f electron. _ _ _ _ _ _ (a ) l = 2; Lz = h l ...h l Lz = 2h , h , 0, h , 2h _ _ _ _ _ _ _ _ _ _ (b ) l = 4; Lz = h l ... h l Lz = 4h , 3h , 2h , h , 0, h , 2h , 3h , 4h 53* If the outer electron in sodium moves in the n = 3 Bohr orbit, the effective nuclear charge would be Ze = 1e, and the energy of the electron would be 13.6 eV/32 = 1.51 eV. However, the ionization energy of sodium is 5.14 eV, not 1.51 eV. Use this fact and Equation 37-45 to calculate the effective nuclear charge Z seen by the outer electron in sodium. Assume that r = 9a 0 for the outer electron. Use Equ. 37-45, assuming r = 9a 0 Z = 9(5.14/13.6) = 3.40 2 2 [Note: If we use the Bohr model: En = (Z) E0/n ] [ Z = 9(5.14/13. 6) = 1.84 ] [The above result indicates that the assumption that r = 9a 0 is not justified.] 54 The optical spectra of atoms with two electrons in the same outer shell are similar, but they are quite different from the spectra of atoms with just one outer electron because of the interaction of the two electrons. Separate the following elements into two groups such that those in each group have similar spectra: lithium, beryllium, sodium, magnesium, potassium, calcium, chromium, nickel, cesium, barium. Lithium, sodium, potassium, chromium, and cesium belong to one group - one outer s electron. Beryllium, magnesium, calcium, nickel, and barium belong to a second group - two outer s electrons.

Chapter 37

Atoms

55 Write down the possible electron configurations for the first excited state of (a ) hydrogen, (b ) sodium, (c) helium. (a ) For H, E depends only on n Lowest excited state: 2s or 2p (b ) For Na, 3p state is higher energy than 3s state Lowest excited state: 1s 22s22p63p (c) For He, lowest excited state has one electron in 2s Lowest excited state: 1s2s 56 Indicate which of the following elements should have optical spectra similar to hydrogen and which should be similar to helium: Li, Ca, Ti, Rb, Hg, Ag, Cd, Ba, Fr, Ra. Atoms with one outer electron have spectra similar to H: Li, Rb, Ag, Fr. Atoms with two outer electrons have spectra similar to He: Ca, Ti, Hg, Cd, Ba, Ra. 57* (a ) Calculate the next two longest wavelengths in the K series (after the Ka line) of molybdenum. (b ) What is the wavelength of the shortest wavelength in this series? 2 (a ) Use Equ. 37-46 with n = 3 and Z = 42; ? = [1240/(41 13.60.889)] nm = 0.0610 nm repeat for n = 4 ? = 0.0610(0.889/0.9375) nm = 0.0578 nm (b ) Repeat part a with n = ? = 0.0542 nm 58 The wavelength of the Ka line for a certain element is 0.3368 nm. What is the element?
Z1 = 1240 = 19; Z = 20 Ca 0.3368 13.6 0.75

Find Z - 1 and Z; see Example 37-8

59

The wavelength of the Ka line for a certain element is 0.0794 nm. What is the element?
Z1 = 1240 = 39; Z = 40 Zr 0.079413.6 0.75

Find Z - 1 and Z; see Example 37-8

60 Calculate the wavelength of the Ka line of rhodium. 2 Use Equ. 37-46 with n = 2 and Z = 45 ? = [1240/(44 13.60.75)] nm = 0.0628 nm 61* Calculate the wavelength of the Ka line in (a ) magnesium (Z = 12) and (b ) copper (Z = 29). 2 (a ) Use Equ. 37-46 with n = 2 and Z = 12 ? = [1240/(11 13.60.75)] nm = 1.00 nm 2 (b ) Use Equ. 37-46 with n = 2 and Z = 29 ? = [1240/(28 13.60.75)] nm = 0.155 nm 62 For the principal quantum number n = 3, what are the possible values of the quantum numbers l and m? l = 0 ... n 1. For n = 3, l = 0, 1, 2. 63 An electron in the L shell means that (a ) l = 0 , (b ) l = 1, (b ) n = 1, (c) n = 2, (d ) m = 2, (e) none of the above are true. (c ) 64 The Bohr theory and the Schrdinger theory of the hydrogen atom give the same results for the energy levels. Discuss the advantages and disadvantages of each model.

Chapter 37

Atoms

The Bohr theory is easier to apply and gives essentially correct results for the energies of the stationary states. However, it gives incorrect results as regards the angular momenta and the spatial distribution of the electron. The Schrdinger theory gives not only the correct energies of the stationary states but also provides information on the angular momenta and probability distribution of electrons. However, the Schrdinger theory is more difficult to use. 65* In Figure 37-17, there are small dips in the ionization-energy curve at Z = 31 (gallium) and Z = 49 (indium) that are not labeled. Explain these dips using the electron configurations of these atoms given in Table 37-1. Zinc (Z = 30) has a configuration of closed subshells, namely 3d104s2; its ionization energy is relatively large. Gallium has one more electron in the 4p state. This electron is less tightly bound; therefore the ionization energy of gallium is relatively small. Likewise for cadmium (Z = 48) with the outer closed subshell configuration of 4d105s2, and indium with one more electron in the 5p state. 66 What is the energy of the shortest wavelength photon emitted by the hydrogen atom? ?min = hc/?E; ?E = 13.6 eV 67 The wavelength of a spectral line of hydrogen is 97.254 nm. Identify the transition that results in this line. Use Equs. 37-18 and 37-15;
1
2 n1

1
2 n2

1240 13.6

1
2 n1

1 n2
2

= 0.9375

Find integers n 1 and n 2. Note n 1 must be 1 in this case.

n 1 = 1, n 2 = 4. The transition is from n = 4 to n = 1.

68 The wavelength of a spectral line of hydrogen is 1093.8 nm. Identify the transition that results in this line. Proceed as in Problem 67 1/n 12 1/n 22 = 0.0833 Find n 1 and n 2 by trial and error n 1 = 3, n 2 = 6. The transition is from n = 6 to n = 3 69* Spectral lines of the following wavelengths are emitted by singly ionized helium: 164 nm, 230.6 nm, and 541 nm. Identify the transitions that result in these spectral lines. 1. Express En for He+; note that Z = 2 En = (413.6/n 2) eV = 54.4/n 2 eV 2. Use Equs. 37-18 and 37-15 to write n 1 and n 2 in 1 1 1240 terms of ? 2 = 2 54.4 n1 n 2 3. By trial and error identify the integers n 1 and n 2 for which ? = 164 nm, 230.6 nm, and 541 nm. For ? = 164 nm, n 2 = 3, n 1 = 2; for ? = 230.6 nm, n 2 = 9, n 1 = 3; for ? = 541 nm, n 2 = 7, n 1 = 4

70 We are often interested in finding the quantity ke2/r in electron volts when r is given in nanometers. Show that ke2 = 1.44 eVnm. From Equ. 37-16 we have ke2/a 0 = 27.2 eV, where a 0 = 0.0529 nm. So ke2 = 1.44 eV.nm. 71 The wavelengths of the photons emitted by potassium corresponding to transitions from the 4P 3/2 and 4P 1/2 states to the ground state are 766.41 nm and 769.90 nm. (a ) Calculate the energies of these photons in electron volts. (b ) The difference in the energies of these photons equals the difference in energy ?E between the 4P 3/2 and 4P 1/2 states in potassium. Calculate ?E. (c) Estimate the magnetic field that the 4p electron in potassium experiences. (a ) hf = (1240/?) eV; ? in nm hf = 1.6179 eV for ? =766.41 nm;

Chapter 37

Atoms hf = 1.6106 eV for ? = 769.90 nm ?E = (1.6179 1.6106) eV = 0.0073 eV B = [0.0073/(25.79105)] T = 63 T

(b ) Find ?E (c) ?E = 2BB

72 To observe the characteristic K lines of the X-ray spectrum, One of the n = 1 electrons must be ejected from the atom. This is generally accomplished by bombarding the target material with electrons of sufficient energy to eject this tightly bound electron. What is the minimum energy required to observe the K lines of (a ) tungsten, (b ) molybdenum, and (c) copper? One 1s electron must be released from the atom. It is shielded from the nuclear charge Z by one other 1s electron. Thus, the effective charge is Z 1, and the ionization energy for that 1s electron is (Z 1)2E0 = Emin. (a ) For tungsten, Z = 74 Emin = 13.6732 eV = 72.5 keV (b ) For molybdenum, Z = 42 Emin = 13.6412 eV = 22.9 keV (c) For copper, Z = 29 Emin = 13.6282 eV = 10.7 keV 73 * The combination of physical constants a = e2k /hc, where k is the Coulomb constant, is known as the finestructure constant. It appears in numerous relations in atomic physics. (a ) Show that a is dimensionless. (b ) Show that in the Bohr model of hydrogen vn = ca/n , where vn is the speed of the electron in the stationary state of quantum number n . _ (a ) Dimension of ke2 is [E][L], where [E] denotes the dimension of energy. (See Problem 70.) The dimension of h _ c is ([E][T])([L]/[T]) = [E][L]. It follows that a = ke2/h c is dimensionless. _ _ (b ) From Equ. 37-9, v = nh /mrn, and using Equ. 37-11 we have v = ke2/h n = ac/n . 74 The positron is a particle identical to the electron except that it carries a positive charge of e. Positronium is the bound state of an electron and positron. (a ) Calculate the energies of the five lowest energy states of positronium using the reduced mass as given by Equation 37-47 in Problem 17. (b ) Do transitions between any of the levels found in (a ) fall in the visible range of wavelengths? If so, which transitions are these? (a ) 1. Determine mr; mpos = me; use Equ. 37-47 mr = me/2 2. Note that En m (see Equ. 37-15) E1 = (13.6/2) eV = 6.8 eV; E2 = 1.7 eV; E3 = 0.756 eV; E4 = 0.425 eV; E5 = 0.272 eV (b ) Visible range: ?E = 1.77 to 3.1 eV No transitions are in the visible range of wavelength 75 The deuteron, the nucleus of deuterium (heavy hydrogen), was first recognized from the spectrum of hydrogen. The deuteron has a mass twice that of the proton. (a ) Calculate the Rydberg constant for hydrogen and for deuterium using the reduced mass as given by Equation 37-47 in Problem 17. (b ) Using the result obtained in (a ), determine the wavelength difference between the longest wavelength Balmer lines of hydrogen and deuterium. (a ) 1. R = 1.097373107 m1 (see Problem 17) RH = 1.096776107 m1 (see text p. 1171) 2. RM = R[M /(me + M ) = R/(1 + me/M ) RD = R/(1 + 0.511/1876.6) = 1.097074107 m1 7 (b ) From Equ. 37-2, ? = n 12n 22/[R(n 12 n 22)]; then ? = [36/(51.09677610 )] m = 656.47 nm ?? = ?[(me/M H) (me/M D)] ?? = (656.472.723104) nm = 0.179 nm 76 The muonium atom is a hydrogen atom with the electron replaced by a particle. The is identical to an

Chapter 37

Atoms

electron but has a mass 207 times as great as the electron. (a ) Calculate the energies of the five lowest energy levels of muonium using the reduced mass as given by Equation 37-47 in Problem 17. (b ) Do transitions between any of the levels found in (a ) fall in the visible range of wavelengths, i.e., between ? = 700 nm and 400 nm? If so, which transitions are these? (a ) 1. Use Equ. 37-47 and 37-15 to find E1 mr = 207me/(1 + 207/1836) = 186me; E1 = 186E0 2 2. En = E1/n E1 = 2.53 keV; E2 = 632.5 eV; E3 = 281.1 eV; E4 = 158.1 eV; E5 = 101.2 eV (b ) For visible range, ?E = 1.77 to 3.1 eV None of the transitions are in the visible range 77 The triton, a nucleus consisting of a proton and two neutrons, is unstable with a fairly long half-life of about 12 years. Tritium is the bound state of and electron and a triton. (a ) Calculate the Rydberg constant of tritium using the reduced mass as given by Equation 37-47 in Problem 17. (b ) Using the result obtained in (a ) and in part (b ) of Problem 75 determine the wavelength difference between the longest wavelength Balmer lines of tritium and deuterium and between tritium and hydrogen. (a ) 1. Evaluate 1 + me/mT and 1 + me/mp mT = (5.008271027 9.111031) kg = 5.00827 kg 1 + me/mT = 1.0001819; 1 + me/mp = 1.0005446 2. RT = RH[(1 + me/mp)/(1 + me/mp)] RT = (1.0967761071.0005446/1.0001819) m1 = 1.097174107 m1 (b ) 1. ?1 = R(1/4 1/9); ? = 7.2/R ?T = 656.2314 nm; ?D = 656.2912 nm; ?H = 656.4695 nm 2. Evaluate the wavelength differences ?D ?T = 0.0598 nm; ?H ?T = 0.2381 nm 78 Suppose that the interaction between an electron and proton were of the form F =Kr, where K is a constant, rather than 1/r2. If the stationary state orbits are again limited by the angular momentum condition L = nh

, what are then the radii of these orbits? Show that for this case the kinetic energies of the stationary states are _ given by E = nh ?, where ? is the angular frequency of the electron about the proton. We have mvnrn = _ _ nh and mvn2/rn = Krn. Solving for rn one obtains rn = [nh / Km ]1/2. The potential energy is given by
U (rn ) = Fdr = Krn2 / 2 . The angular frequency is ? = v/r =
rn

K/m . The total energy is

_ K/m _ 1 Kr 2 = Kr 2 En = 1 2 mv 2 = nh ?. n + n = nh 2 n 79 The frequency of revolution of an electron in a circular orbit of radius r is f rev = v/2pr, where v is the speed. (a ) Show that in the n th stationary state
f rev = k 2 Z 2 e4 m 1 2 h 3 n 3

(b ) Show that when n 1 = n , n 2 = n 1, and n is much greater than 1,

Chapter 37
1 n2 2 1 n2 1 2 n3

Atoms

(c) Use your result in part (b ) and Equation 37-13 to show that in this case the frequency of radiation emitted equals the frequency of motion. This result is an example of Bohrs correspondence principle: when n is large, so that the energy difference between adjacent states is a small fraction of the total energy, classical and quantum physics must give the same results. 4 2 k 2 Z 2 e4 m (a ) Substitute rn from Equ. 37-11 and vn = nh /(2pmrn ) into f rev = vn/2prn. The result is f rev = . h3 n3 2 1 1 n2 n2 ( n2 2n + 1) 2n = 2 1 n2 = (b ) 2 2 = 2 2 2 2 4 3 . n2 n1 n1 n 2 n ( n 2n + 1) n n

(c) From Equs. 37-7 and 37-15, f =

2 2 k 2 Z 2 e4 m 1 1 n2 n2 . Using the result of part (b ) we see that this h3 1 2

reduces to f rev when n 1 = n , n 2 = n 1, and n >> 1.