Chapter 12: From Classical to Quantum Mechanics

Problem numbers in italics indicate that the solution is included in the Students Solutions Manual. Questions on Concepts Q12.1) How did Planck conclude that the discrepancy between experiments and
classical theory for blackbody radiation was at high and not low frequencies? The experimental results and the classical theory agree in the limit of low frequencies and diverge at high frequencies.

Q12.2) The inability of classical theory to explain the spectral density distribution of a
blackbody was called the ultraviolet catastrophe. Why is this name appropriate? The divergence between the classical theory and the experimental results is very pronounced in the UV region. In particular, because the classical theory predicts that the spectral density increases as 2 , the total energy radiated by a blackbody is predicted to be infinite. This prediction was clearly wrong, and the lack of agreement with the experimental results was viewed by scientists of the time as a catastrophe.

Q12.3) Why does the analysis of the photoelectric effect based on classical physics
predict that the kinetic energy of electrons will increase with increasing light intensity? In the classical theory, more light intensity leads to more energy absorption by the solid and the electrons. At equilibrium, as much energy must leave the surface as is absorbed. Therefore, the electrons will have a greater energy. Classical physicists thought that the greater energy would manifest as a higher speed. In fact, it appears as a larger number of electrons leaving the surface with a frequency determined by the photon energy and the work function of the surface.

Q12.4) What did Einstein postulate to explain that the kinetic energy of the emitted
electrons in the photoelectric effect depends on the frequency? How does this postulate differ from the predictions of classical physics? Einstein postulated that the energy of light depends on the frequency, whereas in classical theory, the energy depends only on the intensity and is independent of the frequency. He further postulated that the energy of light could only be an integral multiple of hv.

Q12.5) Which of the experimental results for the photoelectric effect suggests that light
can display particle-like behavior?

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Chapter 12/From Classical to Quantum Mechanics The fact that at very low intensity the incident light is still able to eject electrons, if its frequency is above the threshold frequency, suggests that the energy of the light can be concentrated in a region of atomic dimensions at the surface of the solid. This suggests particle-like behavior.

Q12.6) In the diffraction of electrons by crystals, the volume sampled by the diffracting
electrons is on the order of 3 to 10 atomic layers. If He atoms are incident on the surface, only the topmost atomic layer is sampled. Can you explain this difference? Whereas electrons can penetrate through the topmost layer into the solid, He atoms are too large to allow penetration at thermal energies. Therefore electrons sample a number of atomic layers below the surface, and He atoms are only sensitive to the outermost layer.

Q12.7) In the double-slit experiment, researchers found that an equal amount of energy
passes through each slit. Does this result allow you to distinguish between purely particle-like or purely wave-like behavior? No. This result would be expected for both waves and particles. In the case of particles, the same number would pass through each slit for a large number of incident particles. For a wave, the fraction of the intensity of the wave that passes through each slit would be the same.

Q12.8) Is the intensity observed from the diffraction experiment depicted in Figure 12.6
the same for the angles shown in parts (b) and (c)? Yes. For all minima in a graph of intensity versus frequency, the intensity is zero as seen in Figure 12.5.

Q12.9) What feature of the distribution depicted as Case 1 in Figure 12.7 tells you that the broad distribution arises from diffraction?
The intensity goes through a minimum and increases again on both sides of the maximum. This can only occur through wave interference.

Q12.10) Why were investigations at the atomic and subatomic levels required to detect
the wave nature of particles? The wavelength of particles with greater mass is so short that particle diffraction could not be observed experimentally. Therefore, the wave-particle duality present even in heavier particles was not observed.

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Chapter 12/From Classical to Quantum Mechanics

Problems P12.1) The distribution in wavelengths of the light emitted from a radiating blackbody is
a sensitive function of the temperature. This dependence is used to measure the temperature of hot objects, without making physical contact with those objects, in a technique called optical pyrometry. In the limit (hc k T ) >> 1, the maximum in a plot of ( , T ) versus is given by max = hc / 5kT . At what wavelength does the maximum in

( ,T ) occur for T = 450, 1500, and 4500 K?

According to Example Problem 14.1, max =

hc . 5k T

6.626 1034 J s 2.998 108 m s 1 = 6.40 106 m at 450 K. max for 1500 K and 5 1.381 1023 J K 1 450 K 4500 K is 1.92 106 m and 6.39 107 m, respectively.

max =

P12.2) For a monatomic gas, one measure of the average speed of the atoms is the
root mean square speed, v rms = v 2
3kT , in which m is the molecular mass and k is m the Boltzmann constant. Using this formula, calculate the de Broglie wavelength for He and Ar atoms at 100 and at 500 K.
1 2

h = mv rms

h = 3k T m

6.626 1034 J s 3 1.381 1023 J K 1 100 K 4.003amu 1.661 1027 kg amu 1

= 1.26 1010 m for He at 100 K. =5.65 1011 m for He at 500 K. For Ar, = 4.00 1011 m and 1.79 1011 m at 100 K and 500 K, respectively.

P12.3) Using the root mean square speed, v rms = v 2

3kT , calculate the gas m temperatures of He and Ar for which = 0.20 nm, a typical value needed to resolve diffraction from the surface of a metal crystal. On the basis of your result, explain why Ar atomic beams are not suitable for atomic diffraction experiments.
1 2

For He, h2 T= 3k m 2

( 6.626 10
3 1.381 10
23 1

34

J s)

J K 4.003amu 1.661 10

27

kg amu ( 0.20 10 m )
1 9

= 40 K

For Ar, T = 4.0 K.

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Chapter 12/From Classical to Quantum Mechanics The argon temperature is well below its liquifaction temperature at 4 K. It will not be possible to make an atomic beam of Ar atoms with this wavelength with conventional means.

P12.4) Electrons have been used to determine molecular structure by diffraction.

Calculate the speed of an electron for which the wavelength is equal to a typical bond length, namely, 0.150 nm. p h 6.626 1034 J s v= = = = 4.85 106 m s 1 31 9 m m 9.109 10 kg 0.150 10 m

same energy as an infrared photon ( = 104 nm), a visible photon ( = 500 nm), an ultraviolet photon ( = 100 nm), and an X-ray photon ( = 0.1 nm). What temperature would the gas have if it had the same energy as each of these photons? Use the root mean 1 3kT , for this calculation. square speed, v rms = v 2 2 = m v= 2E = m
4

P12.5) Calculate the speed that a gas-phase oxygen molecule would have if it had the

2hc = m

2 6.626 1034 Js 2.998 108 m s 1 32.0 amu 1.661 10

27

kg ( amu ) 10000 10 m
1 9

= 864 m s 1 for

= 10 nm.The results for 500 nm, 100 nm and 0.1 nm are 3.87 103 m s1, 8.65 103 m
s1, and 2.73 105 m s1. We calculate the temperature using the formula
2

1 1 2 M v rms 32.0 kg mol ( 864 m s ) T= = = 958 K 3R 3 8.314 J mol1 K 1 = 104 nm. The results for 500 nm, 100 nm and 0.1 nm are 1.92 104 K, 9.60 104 K, and 9.56 107 K.

P12.6) Pulsed lasers are powerful sources of nearly monochromatic radiation. Lasers
that emit photons in a pulse of 10-ns duration with a total energy in the pulse of 0.10 J at 1000 nm are commercially available. a) What is the average power (energy per unit time) in units of watts (1 W = 1 J/s) associated with such a pulse? b) How many 1000-nm photons are emitted in such a pulse? a) P =

E 0.10 J = = 1.0 107 J s 1 8 t 1.0 10 s E E 0.10 J b) N = pulse = pulse = = 5.0 1017 1 8 c 2.998 10 m s E photon h 6.626 1034 J s 1 1.000 106 m

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Chapter 12/From Classical to Quantum Mechanics

P12.7) Assume that water absorbs light of wavelength 3.00 106 m with 100%
efficiency. How many photons are required to heat 1.00 g of water by 1.00 K? The heat capacity of water is 75.3 J mol1 K1. hc = n C p , m T E = Nh = N
1.00g 75.3J K 1 mol1 1.00 K 3.00 106 m m C p , m T = = 6.311019 N= 1 34 1 8 18.02g mol 6.626 10 J s 2.998 10 m s M hc

P12.8) A 1000-W gas discharge lamp emits 3.00 W of ultraviolet radiation in a narrow
range centered near 280 nm. How many photons of this wavelength are emitted per second? E 3.00 W 1J s 1W 1 3.00 W 1J s 1W 1 n = total = = = 4.23 1018 s 1 hc 6.626 1034 J s 2.998 108 m s 1 E photon 280 109 m

P12.9) A newly developed substance that emits 225 W of photons with a wavelength of
225 nm is mounted in a small rocket such that all of the radiation is released in the same direction. Because momentum is conserved, the rocket will be accelerated in the opposite direction. If the total mass of the rocket is 5.25 kg, how fast will it be traveling at the end of 365 days in the absence of frictional forces? The number of photons is given by 1 J s 1 1 J s 1 3.00 W 225 W E W = W n = total = = 2.547 1020 s 1 34 8 1 hc 6.626 10 J s 2.998 10 m s E photon 225 109 m The momentum of one photon is h 6.626 1034 J s p= = = 2.945 1027 kg m s 1 225 109 m The force is given by the rate of change of momentum. d ( np ) = 2.945 1027 kg m s 1 2.547 1020 s 1 = 7.501107 kg m s 2 F= dt The final speed is given by F 7.501107 kg m s 2 86400s v = v0 + at = t = 365days = 4.51m s 1 m 5.25 kg day

P12.10) What speed does a H2 molecule have if it has the same momentum as a photon
of wavelength 280 nm?

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Chapter 12/From Classical to Quantum Mechanics

p= h = mH 2 v H 2 h mH 2 = 6.626 1034 J s 2.016 amu 1.6611027 kg ( amu ) 280 109 m
1

vH2 =

= 0.707m s 1

P12.11) The following data were observed in an experiment of the photoelectric effect from potassium: 4.49 3.09 1.89 1.34 7.00 1019 Kinetic Energy (J) Wavelength 250 300 350 400 450 (nm)
Graphically evaluate these data to obtain values for the work function and Plancks constant.
410 310
E (J)
-19 -19 -19 -19

3.11 500

210 110

2.510

310
1

3.510

410

The best-fit line is given by E = 3.97362 1019 + 2.111711025

2.111711025 J m 7.0 1034 J s. The work function is 2.998 108 m s 1 hc E where given by the intercept of the line with the x axis at y = 0. = Because the slope is hc, h =

0=

2.1171? 0 J m =5.30? 07 m. This gives 4.0 1019 J or 2.5eV. 19 3.97362? 0 J

25

P12.12) Show that the energy density radiated by a blackbody

Etotal ( T ) V = ( , T ) d =
0

8 h 3 1 d depends on the temperature as T 4. (Hint: hv / kT 3 1 c e 0

x3 4 dx = . e x 1 15 0 Using your result, calculate the energy density radiated by a blackbody at 800 and 4000 K.

Make the substitution of variables x = h / kT . ) The definite integral

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Chapter 12/From Classical to Quantum Mechanics

Etotal 8 h 3 1 h = ; dx = d d . Let x = h h 3 kT kT V c 0 e kT 1
8 h 3 1 8 k 4T 4 d = c3 eh kT 1 h 3c3 0

x3 8 5 k 4T 4 dx = ex 1 15 h 3 c 3 0

At 800 K, At 4000,

Etotal 8 5 k 4T 4 8 5 (1.3811023J K 1 ) 4 (800 K) 4 = = = 3.10 104 J m 3 3 3 3 3 15 h c V 15 ( 6.626? 034 J s ) ( 2.998 108 m s 1 ) Etotal 8 5 (1.3811023 J K 1 ) 4 (4000 K) 4 = = 0.194 J m 3 3 34 8 1 3 V 15 ( 6.626 10 J s ) ( 2.998 10 m s )

P12.13) The power per unit area emitted by a blackbody is given by

P = T 4 with = 5.67 ? 108 W m 2 K 4 . Calculate the energy radiated by a spherical blackbody of radius 0.500 m at 1000 K per second. What would the radius of a blackbody at 2500 K be if it emitted the same energy as the spherical blackbody of radius 0.500 m at 1000 K? 2 4 E = A T 4 =4 ( 0.500 m ) 5.67 10 8 J s 1 m 2 K 4 (1000 K ) = 1.78 105 J s 1

Because the total energy radiated by the spheres must be equal, 4 r12 T14 =4 r22 T24
r2 = r12T14 = T24

( 0.500 m ) (1000 K ) 4 ( 2500 K )

2

= 0.0800 m

P12.14) In our discussion of blackbody radiation, the average energy of an oscillator

E osc = e h
kT h

was approximated as E osc = E Eapprox

1 + h

1 kT )

= kT for h

kT

<< 1 .

Calculate the relative error =

in making this approximation for E = 4 1012 s1 at temperatures of 6000, 2000, and 500 K. Can you predict what the sign of the relative error will be without a detailed calculation?

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Chapter 12/From Classical to Quantum Mechanics h kT exp h 1 kT = h exp h 1 kT

Relative Error =

E Eapprox E

34 12 1 6.626 10 J s 4.00 10 s h 1.3811023 J K 1 6000 K kT 12 1 34 6.626 10 J s 4.00 10 s h exp kT 1 exp 1.3811023 J K 1 6000 K 1 = 34 12 1 h 6.626 10 J s 4.00 10 s 1 34 12 1 exp h 1 6.626 10 J s 4.00 10 s exp 23 1 kT 1.38110 J K 6000 K = 0.0162 for T = 6000 K. E The results for 2000 K, and 500 K are 0.0496 and 0.219. E Eapprox is always a negative number. Because Eapprox = kT > E, the relative error = E Relative Error = E Eapprox

P12.15) The power (energy per unit time) radiated by black body per unit area of
surface expressed in units of W m2 is given by P = T 4 with = 5.67 108 W m 2 K 4 . The radius of the sun is 7.00 105 km and the surface temperature is 6000 K. Calculate the total energy radiated per second by the sun. Assume ideal blackbody behavior. E = PA = T 4 4 r 2
= 5.67 108 W m 2 K 4 ( 6000 K ) 4 ( 7.00 108 m )
4 2

= 4.52 1026 W

P12.16) A more accurate expression for E osc would be obtained by including additional terms in the Taylor-Mclaurin series. The Taylor-Mclaurin series expansion of f(x) in the vicinity of x0 is given by (see Math Supplement) 1 d 2 f ( x) 1 d 3 f ( x) d f ( x) 3 f ( x) = f ( x0 ) + ( x x0 ) + ( x x0 ) 2 + ( x x0 ) + ... d x x = x0 2! d x 2 x = x 3! d x 3 x = x
0 0

Use this formalism to better approximate E osc by expanding e to ( h kT )

3

in powers of h kT out E osc kT in the vicinity of h kT = 0. Calculate the relative error, , if you E osc
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h kT

Chapter 12/From Classical to Quantum Mechanics had not included the additional terms for = 1.00 1012 s1 at temperatures of 800, 500, and 250 K. 2 3 h h 1 h 1 h kT The Taylor series expansion of e is 1 + + + + ... . Therefore kT 2 kT 6 kT including terms up to h

E osc =

h
2

, kT )
3

h 1 h 1 h + + kT 2 kT 6 kT Eosc kT h = kT h 1 h 2 1 h 3 Eosc + + kT 2 kT 6 kT

h h 1 h 1 h + + kT 2 kT 6 kT
2 3

6.626 1034 J s 1.00 1012s 1 1 6.626 1034 J s 1.00 1012s 1 2 + 1.3811023 J K 1 800 K 2 1.3811023 J K 1 800 K Eosc kT 23 1 = 6.626 1034 J s 1.00 1012s 1 1.38110 J K 800 K 3 Eosc 1 6.626 1034 J s 1.00 1012s 1 + 6 1.3811023 J K 1 800 K 34 12 1 34 12 1 2 6.626 10 J s 1.00 10 s 1 6.626 10 J s 1.00 10 s + 1.3811023 J K 1 800 K 2 1.3811023 J K 1 800 K 34 12 1 6.626 10 J s 1.00 10 s 3 1 6.626 1034 J s 1.00 1012s 1 + 6 1.3811023 J K 1 800 K

Eosc kT = 0.0306 for 800 K. The corresponding values for 500 K and 250 K are Eosc 0.0495 and 0.102.

P12.17) The observed lines in the emission spectrum of atomic hydrogen are given by
% ( cm 1 ) = RH ( cm 1 )
1 1 2 cm 1 , n > n1 . In the notation favored by spectroscopists, 2 n1 n

E and RH = 109, 677 cm 1. The Lyman, Balmer, and Paschen series refers to hc n1 = 1, 2, and 3, respectively, for emission from atomic hydrogen. What is the highest % value of v and E in each of these series? 1 % 0. Therefore The highest value for corresponds to n 1 % = RH 2 cm 1 = 109, 677 cm 1 or Emax = 2.18 1018 J for the Lyman series. 1 1 % = RH 2 cm 1 = 27419 cm 1 or Emax = 5.45 1019 J for the Balmer series, and 2

% =

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Chapter 12/From Classical to Quantum Mechanics

% = RH 2 cm 1 = 12186 cm 1 or Emax = 2.42 1019 J for the Paschen series 3

P12.18) A beam of electrons with a speed of 3.50 104 m/s is incident on a slit of width
200 nm. The distance to the detector plane is chosen such that the distance between the central maximum of the diffraction pattern and the first diffraction minimum is 0.500 cm. How far is the detector plane from the slit? The diffraction minima satisfy the condition sin =

minimum is at sin = . We choose the plus sign (the minus sign gives the distance a from the slit in the opposite direction) giving h 6.626 1034 J s sin = = = = 0.10392 a mva 9.109 1031kg 3.50 104 m s 1 200 109 m = 5.97 degrees The distance d from the screen and the position of the first minimum s are related by s 0.500 cm = = 4.78cm. d= tan 0.1045

n , n = 1, 2,... and the first a

P12.19) If an electron passes through an electrical potential difference of 1 V, it has an energy of 1 electron-volt. What potential difference must it pass through in order to have a wavelength of 0.100 nm?
h 1 1 h2 E = me v 2 = me = 2 2 2me 2 me = 2 9.109 1031kg (1010 m )
2

( 6.626 10

34

J s)

2 2

= 2.411017 J

1eV = 150.4 eV 1.602 1019 J

The electron must pass through an electrical potential of 150.4 V.

P12.20) What is the maximum number of electrons that can be emitted if a potassium surface of work function 2.40 eV absorbs 3.25 103 J of radiation at a wavelength of 300 nm? What is the kinetic energy and velocity of the electrons emitted? c 6.626 1034 J s 2.998 108 m s 1 1.602 1019 J E = h = 2.40 eV = 2.77 1019 J 9 300 10 m eV
v= 2E = m 2 2.77 1019 J = 7.80 105 m s 1 31 9.109 10 kg

Etotal Etotal 3.25 103 J = = = 4.91 1015 n= 34 8 1 9 E photon hc ( 6.626 10 J s 2.998 10 m s ) 300 10 m electrons.

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Chapter 12/From Classical to Quantum Mechanics

P12.21) The work function of platinum is 5.65 eV. What is the minimum frequency of
light required to observe the photoelectric effect on Pt? If light with a 150-nm wavelength is absorbed by the surface, what is the velocity of the emitted electrons? a) For electrons to be emitted, the photon energy must be greater than the work function of the surface. 1.602? 019 J = 9.05 1019 J E = h 5.65 eV eV 19 E 9.05 10 J 1.37 1015 s 1 34 h 6.626 10 J s b) The outgoing electron must first surmount the barrier arising from the work function, so not all the photon energy is converted to kinetic energy. hc Ee = h =

6.626 10 J s 2.998 108 m s 1 9.05 1019 J = 4.19 1019 J 9 150 10 m 2 Ee 2 4.19 1019 J = = 9.59 105 m s 1 31 9.11 10 kg me

34

v=

P12.22) X-rays can be generated by accelerating electrons in a vacuum and letting them
impact on atoms in a metal surface. If the 1000-eV kinetic energy of the electrons is completely converted to the photon energy, what is the wavelength of the X-rays produced? If the electron current is 1.50 105 A, how many photons are produced per second? hc 6.626 1034 J s 2.998 108 m s 1 = = = 1.24 nm 1.602 1019 J E 1000 eV eV current 1.50 105Cs 1 n= = = 9.36 1013 s 1. 19 charge per electron 1.602 10 C

P12.23) When a molecule absorbs a photon, both the energy and momentum are
conserved. If a H2 molecule at 300 K absorbs an ultraviolet photon of wavelength 100 nm, what is the change in its velocity v ? Given that its average speed is v rms = 3kT / m , what is v / v rms ? Because momentum is conserved, p photon = h = 6.626 1034 J s = 6.626 1027 kg m s 1 9 100 10 m

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Chapter 12/From Classical to Quantum Mechanics

All this momentum is transferred to the H2 molecule pH 2 = 6.626 1027 kg m s 1 = mv

v H 2 = 6.626 1027 kg m s 1 = 1.98 m s 1 2.016 amu 1.6611027 kg/amu 1.98 m s 1 3 8.314 J mol K 298 K 2.016 103 kg mol1
1 1

v 1.98 m s 1 = = v 3RT M

= 1.03103

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