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Homework1 Answer Key Quantum Chemistry
Homework1 Answer Key Quantum Chemistry
Homework1 Answer Key Quantum Chemistry
expressed in cm1 .
Answer: Energy of a photon of wavelength or frequency or wavenumber is given by
hc
E = h = hc
= . For = 200 cm1 , = 1.50 1015 Hz, and = 5.00 104 cm1 .
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 =
n=0
n=
X
n=0
.
Pn
(1)
Pn is the probability
that the system has energy En and is given by the Arrhenius factor,
En
, where T is the temperature. This concept can be applied to calculating
Pn = exp
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.
(a) Show that hEi can be expressed as
function of a system defined as:
Z=
n=
X
d ln Z
1
, where =
and Z is the partition
d
kB T
Pn =
n=0
n=
X
exp
n=0
nh
kB T
d ln Z
d ln Z
= hEi, rather trying to show that hEi =
.
d
d
(b) Z is a convergent series and converges to
n=
X
1
1
nh
=
=
,
Z=
exp
h
kB T
1 exp (h)
n=0
1 exp
kB T
(2)
(3)
because exp (h) < 1. Using the equation you derived in the previous part, show that
hEi =
h
exp (h) 1
(4)
Answer:
(a)
ln Z = ln
n=
X
exp (nh)
(5)
n=0
d ln Z
= n=
X
d
exp (nh)
n=
X
(6)
n=0
n=0
(b)
Z = (1 exp (h))1
d ln (1 exp (h))1
d ln Z
hEi =
=
d
d
1
= (1 exp (h))
( exp (h)) (h)
(1 exp (h))2
h exp(h)
h
=
=
1 exp(h)
exp(h) 1
2
(7)
(8)
(9)
(10)
8 2
8h 3
(where U is the
hEi
=
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 electromagnetic 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 electromagc
netic wave from classical equipartition theorem.
b
3
, where a and b are empirical constants.
(b) Wiens equation: U (, T ) = a exp
T
Answer:
(a) At low frequencies, h << kB T . Therefore
x << 1, at low frequencies,
U (, T ) =
h
= h << 1. Since exp(x) 1 + x for
kB T
8h 3
8h 3
8h 3
8 2
=
=
=
kB T .
c3 (exp (h) 1)
c3 (1 + h 1)
c3 h
c3
(11)
h
= h >> 1. Consequently, exp(h) >>
kB T
1, and exp(h) 1 exp(h). Therefore, at high frequencies,
U (, T ) =
8h 3
8h 3 exp (h)
=
c3 (exp (h) 1)
c3
(12)
This form is the same as that of Wiens equation with the empirical constants given by,
h
8h
.
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 ),
4
(13)
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)
exp(x) 1
15
0
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 temperature 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
= 5.525 1019 J = 3.45 eV.
is given by Tmax =
(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
pure , and Tmax impure =
impure . Therefore
(c) impure < pure . Tmax pure =
1
1
RH
4RH