Chem 570: Quantum Chemistry and Spectroscopy

Homework 1: Due by 5 pm on Friday, August 28, 2015

Instructor: Sharani Roy

September 8, 2015

List of constants

1. Velocity of light: c = 2.99792458 108 ms1

2. Boltzmann constant: kB = 1.380658 1023 JK1

3. Plancks constant: h = 6.6260755 1034 Js

4. Wiens displacement constant: 2.90 103 m.K

5. Stefan-Boltzmann constant: = 5.67051 108 Jm2 K4 s1

Questions

1. Calculate the values of frequency () and spatial frequency (

) for ultraviolet radiation with
1
= 200 nm. The spatial frequency or spectroscopic wavenumber is defined as = and is

expressed in cm1 .
Answer: Energy of a photon of wavelength or frequency or wavenumber is given by
hc
= . For = 200 cm1 , = 1.50 1015 Hz, and = 5.00 104 cm1 .
E = h = hc

2. Calculate the energy (in J and in eV) of one photon of visible radiation whose wavelength is
600 nm.
hc
Answer: Energy of a photon of wavelength is given by E = . For = 600 nm, E =

3.3107 1019 J = 2.067 eV.

3. The average energy of a system with allowed energies En = nh, where n is an integer 0,
is given by
n=
X
Pn En
n=0
hEi = n= . (1)
X
Pn
n=0

1
Pn is the probability
 that the system has energy En and is given by the Arrhenius factor,
En
Pn = exp , where T is the temperature. This concept can be applied to calculating
kB T
any average property of a system. For example, you could calculate the average grade of a
class of 10 students, in which three students have earned 80 points and 7 students have earned
90 points.
d ln Z 1
(a) Show that hEi can be expressed as , where = and Z is the partition
d kB T
function of a system defined as:
n= n=  
X X nh
Z= Pn = exp (2)
n=0 n=0
kB T

d ln Z d ln Z
Hint: Show that = hEi, rather trying to show that hEi = .
d d
(b) Z is a convergent series and converges to
n=  
X nh 1 1
Z= exp =  = , (3)
kB T h 1 exp (h)
n=0 1 exp
kB T
because exp (h) < 1. Using the equation you derived in the previous part, show that
h
hEi = (4)
exp (h) 1

Answer:
(a)
n=
X
ln Z = ln exp (nh) (5)
n=0
n=
d ln Z 1 X
= n= (nh exp (nh)) = hEi. (6)
d X
n=0
exp (nh)
n=0

(b)

Z = (1 exp (h))1 (7)

d ln (1 exp (h))1
 
d ln Z
hEi = = (8)
d d
1
= (1 exp (h)) ( exp (h)) (h) (9)
(1 exp (h))2
h exp(h) h
= = (10)
1 exp(h) exp(h) 1

2
 8 2 8h 3
4. Show that Plancks radiation law, U (, T ) = hEi = (where U is the
c3 c3 (exp (h) 1)
energy density at frequency ) reduces to Rayleigh-Jeans Law at low frequencies and Wiens
8 2
equation at high frequencies. is the number of electromagnetic waves at frequency
c3
emitted per unit volume by a perfect blackbody. hEi is the average energy of an electromag-
netic wave. Planck applied the quantum hypothesis that an electromagnetic wave can only
have energy En = nh, where n is an integer 0.
8 2
(a) Rayleigh-Jeans Law: U (, T ) = 3 kB T . kB T is the average energy of an electromag-
c
netic wave from classical equipartition theorem.
 
3 b
(b) Wiens equation: U (, T ) = a exp , where a and b are empirical constants.
T
Answer:
h
(a) At low frequencies, h << kB T . Therefore = h << 1. Since exp(x) 1 + x for
kB T
x << 1, at low frequencies,

8h 3 8h 3 8h 3 8 2
U (, T ) = = = = kB T . (11)
c3 (exp (h) 1) c3 (1 + h 1) c3 h c3

h
(b) At high frequencies, h >> kB T . Therefore = h >> 1. Consequently, exp(h) >>
kB T
1, and exp(h) 1 exp(h). Therefore, at high frequencies,

8h 3 8h 3 exp (h)
U (, T ) = = (12)
c3 (exp (h) 1) c3
This form is the same as that of Wiens equation with the empirical constants given by,
8h h
a = 3 and b = .
c kB
5. The Stefan-Boltzmann law states that the irradiance (radiated power per unit square area)
of a perfect blackbody is proportional to the fourth power of temperature: I = T 4 . Derive
the Stefan-Boltzmann law from Plancks radiation law and calculate the Stefan-Boltzmann
constant, . Compare your calculated value of to the empirical value of .
c
P (, T ) = U (, T ), (13)
4
where P(, T) is the radiated power per unit square area at frequency . Hint: Irradiance is
the power per unit square area of the total spectrum of the blackbody, i.e., over all frequencies.
Use the standard integral: Z
x3 dx 4
= (14)
0 exp(x) 1 15
Answer: Please refer to Example 1-2 in Chapter 1 of the course textbook.

3
6. At what wavelength does the maximum in the energy-density distribution function for a
blackbody occur if (a) T = 300 K, (b) T = 3000 K, and (c) T = 10,000 K.
Answer: Using the Wien displacement law, max T = 2.90 103 mK, (a) max = 9666.67
nm for T = 300 K, (b) max = 966.67 nm for T = 3000 K, and (c) max = 290 nm for T =
10,000 K.

7. Sirius, one of the hottest known stars, has approximately a blackbody spectrum with max =
260 nm. Estimate the surface temperature of Sirius.
Answer: Using the Wien displacement law, max T = 2.90 103 mK, the surface tempera-
ture of Sirius is 11,153.85 K.

8. The work function of very pure Na is 2.75 eV. (a) Calculate the maximum kinetic energy (in
J and eV) of photoelectrons emitted from Na exposed to 200 nm ultraviolet radiation. (b)
Calculate the longest wavelength that will cause the photoelectric effect in pure Na. (c) The
work function of sodium that has not been very carefully purified is substantially less than
2.75 eV, because of adsorbed sulfur and other substances derived from atmospheric gases.
When impure Na is exposed to 200-nm radiation, will the maximum photoelectron kinetic
energy be less than or greater than that for pure Na exposed to 200-nm radiation?
Answer:

(a) According to Einsteins explanation of the photoelectric effect, the maximum kinetic
energy (Tmax ) of photoelectrons emitted from Na exposed to 200 nm ultraviolet radiation
hc
is given by Tmax = = 5.525 1019 J = 3.45 eV.

(b) The longest wavelength (max ) corresponds to the minimum photon energy required to
hc
eject an electron from the metal, and is given by max = = 450.85 nm.

hc hc
(c) impure < pure . Tmax pure = pure , and Tmax impure = impure . Therefore

Tmax impure > Tmax pure .

9. The series in the He+ spectrum that corresponds to the set of transitions where the electron
falls from higher levels into the n = 4 states is called the Pickering series, an important series
in solar astronomy. Derive the formula for the wavelengths of the observed lines in this series.
In what region of the spectrum do they occur?
Answer: First, derive the formula for the energy of an electron in the nth orbit of the
He+ ion (Z = 2) just like Bohr derived the formula for the energy of an electron in the
4RH hc
nth orbit of the H atom. We find that En = , where RH is the Rydberg constant.
n2
Therefore the wavenumber of radiation  emitted  when an electron falls from n1 > 4 into
1 1
n2 = 4 is given by n1 >4n2 =4 = 4RH . The corresponding wavelength is given by
16 n22
1
n1 >4n2 =4 =   . This is the Pickering series. The series starts at n1 =5n2 =4 =
1
4RH 16 n12
2

4
  
1 1 RH
4RH = 9870.98 cm1 = 1013.1 nm, and converges to = = 27419.4 cm1 =
16 25 4
364.7 nm. Therefore it occurs in the near-IR to visible regions of the electromagnetic spectrum
(visible region 390-700 nm).

10. Using the Bohr theory, calculate the ionization energy of He+ in eV and in kJ/mol.
Answer: According to the Bohr theory, the energy of an electron in the nth orbit of the He+
4RH hc
ion is given by En = , where RH is the Rydberg constant. The ionization energy
n2
is the energy required to remove an electron from He+ . From the point of view of the Bohr
theory, it is the energy required to excite the electron from n = 1 to n = . Therefore, the
ionization energy is equal to hc n=1n= = 4RH hc = 438710.4 cm1 = 5248.15 kJ/mol =
54.39 eV.