induced emission the equation is particularly relevant to laser design.

Worked example 2.1

Question. For temperatures of 25 % C and 1000 % C, calculate the ratio of molecules in a typical
excited rotational, vibrational and electronic energy level to that in the lowest energy level,
assuming that the levels are 30 cm71, 1000 cm CHM201
71
and 40Introduction Part above the
000 cm71, respectively,
lowest energy level. [Three significant figures are sufficient. Assume that, for the excited
Problem
rotational level, the1.rotational
Calculate the ratio
quantum of molecules
number J is 4, and in the lowest
remember that two level is levels at 25 oC for
each energy
the following
ð2 J þ 1Þ-fold degenerate.three cases.
Assume Assume
that the thatand
vibrational theelectronic
energy energy
spacing between
levels are non- the two levels are
-1 -1 -1
30 cm , 1000 cm and 40000 cm , respectively; In the first case, the excited level has a
degenerate.]
“2J+1” degeneracy with a “J” value of 4. What will be the effect if the temperature is
Answer. Using Equation o(2.11) for the rotational energy level with J ¼ 4, and the Planck
raised to 1000 C in each case.
relation between energy and wavenumber of Equation (2.2), we have
! "
Nn NJ 2J þ 1 hc~n
¼ ¼ exp $
Nm N0 1 kT
! "
6:626 ' 10$34 J s ' 2:998 ' 1010 cm s$1 ' 30 cm$1
¼ 9 exp $
1:381 ' 10$23 J K$1 ' 298 K
¼ 7:79 at 25 % C ð298 KÞ
2.2 ABSORPTION
and 8:70 at 1000 % C ð1273 KÞAND EMISSION OF RADIATION 31

For the vibrational energy level:

(Remember that exponentials and logarithms have no units so that the units of this exponential
must cancel.) ! "
Nv 6:626 # 10"34 # 2:998 # 1010 # 1000
¼ exp "
N0 1:381 # 10"23 # 298
¼ 8:01 # 10"3 at 25 $ C
¼ 0:323 at 1000 $ C

For the electronic energy level:

! "
Ne 6:626 # 10"34 # 2:998 # 1010 # 40 000
¼ exp "
N0 1:381 # 10"23 # 298
¼ 1:40 # 10"84 at 25 $ C
¼ 2:35 # 10"20 at 1000 $ C

These calculations show how rotational energy levels are much more heavily populated than
are vibrational energy levels which, in turn, are much more heavily populated than electronic
Problem 2. Which
energy levels – indeed,ofatthese moleculesthere
room temperature, will is
show
zero a pure rotational
population of a typical(microwave)
electronic spectrum:
CH 4, CH
energy 3Cl, CH
level. The 2Cl 2, CHCl3,also
calculations CHshow
2=CHhow 2, benzene, SF6? increase with increasing
the populations
temperature so that, at very high temperatures, populations of electronic states can become
CH 3Cl, and
important. ForCH 2Cl2 (Only
example, these molecules
the temperature of hydrogen areatomshaving permanent
in the exterior dipolemoment)
(the photosphere) of
a star can be of the order of 6000 K. The interior of the star acts as continuum source of
radiation and
Problem 3. the huge path
Without length of absorbing
calculating the specificatoms, togetherarrange
values, with theirthe
highfollowing
temperature,
molecules in
order of increasing value of their rotational constants, B : HF, DF, HD, 12Cof
results in the Balmer series being observed in absorption due to the appreciable population 16
O, 13C16O,
12the18
n ¼ 2 level.
C O. (Hint: The interatomic distances in pm for some of the molecules are as follows:
HF – 91.70; HD – 7.14; 12C16O – 113.10)

The
The order willcoefficients
Einstein be HD > HF DF > 12
are>related 16
toCthe > 13C
Owave 16
O > 12c
functions Cm18and
O cn of the combining
Reason
states B isthe
through inversily moment Rnmto
transitionproportional , areduced mass given
vector quantity by (internuclear distance, r)2
(µ) and
Lower the bond distance and reduced mass, higher will be the rotational constant.
ð
nm
R
Problem 4.Classify each of the following ¼ c*n m c m dt
molecules as linear, spherical, ð2:13Þ
symmetric, or
asymmetric top molecules:
a) CH4 b) CH3F c) CH3D d) SF6 e) SF5Br f) HCN g) H2O2 h) CH2=CH2
for interaction with the electric component of the radiation. The quantity m is the electric
dipole moment operator, and
a) CH4 – Spherical Top (Ia = Ib = Ic)
b) CH3F – Prolate symmetrical Top (IaP< Ib = Ic)
m ¼ qi ri ð2:14Þ
i

where qi and ri are the charge and position vector of the ith particle (electron or nucleus).
The transition moment can be thought of as the oscillating electric dipole moment due to the
transition. Figure 2.3 shows the p and p* molecular orbitals of ethylene and, if an electron is
 1. Molecules 2ν 2k BT ln 2dipole moment
δν δλ show pure rotational microwave
b) Withwith
δν =a permanent and = solve for T:
c m ν λ
spectra:
2 2
2k T ln 2  δν ⋅ c 
a) H2,BNo b)=HCl,  δλ c   Cl, m 
 Yes c) TCH
 ⇒ = 4, No⋅ d) CH
⋅  3 Yes f) H2O, Yes
 where
m  ν ⋅2   λ 2   2k B ln 2 
c)g)CH
H32D
O2–, Prolate
Yes h)symmetrical
NH3, Yes Top (Ia < Ib = Ic)
d) SF6 – Spherical Top (Ia = Ib = Ic)
e)Molecules
SFm5Br – )Prolate  1kg Top  (I
6.022 × 10I 23) 
2. (48 Ti =with ⋅symmetrical
mol −1 
48 ganisotropic a < Ib =show
polarizability
 c
 =pure
7.971 × 10 −26 kg Raman spectra:
rotational
f) HCN – Linear symmetrical 1000 g
 Top  1mol
(Ia = 0; Ib = Ic) 
g)(Note:
H2O2 –asAsymmetrical
a general symmetrical Top2 (Ia ≠ Ib ≠ are Ic) Raman
h) CH  61.8
=CH – × 10−12 mrule,
Asymmetrical 3.0spherical
108 m ⋅ s −1molecules
×symmetrical  Top (Ia ≠7.971 −26 and microwave inactive.)
Ib ≠ I×c)10 kg 
T=
2
 2 ⋅   ⋅ 
 654.2
a) H2, Yes 10 −9 m
b)×HCl, Yes c) CH 2 , No d) CH2(1.381 × 1023 J ⋅ K −1 ) ln 2 
4 3Cl, Yes e) CH2Cl2, Yes
T = 8.360
Problem × 105 K the
5. Estimate = 836, 000 Kof a state that gives rise to a line of width
lifetime
f) CH3a)
CH0.1
3, Yes −1g) SF6, No −1
cm b) 1 cm and c) 100 MHz.
1 1 1
7. 3. δν ⇒ τdiatomic
For= a linear = and ν = ν c therefore
the selection rule is ΔJτ ==±2. This. means the separation
2πτ 2πδν 2π c δν
between the Stokes lines becomes:
1 1
a) τ = = = 5.31× 10 −11 s = 53.1 ps
J ,J 2
2π c δν
i B(2J
2π (3.0 × 1010
3) i B(2(J 2) 3)cm ⋅ s −1
)(0.1cm −1
)
2BJ 3B 2BJ 4B 3B 4B

b) The lifetime hthat corresponds

h
to a 1 cm-1 linewidth
h
is 5.31 ps.
4B 4 2
rCl Cl
c) The lifetime 8 that 2 2c r2
cI corresponds 2 2 c linewidth is 1.6 ns.
to a 100MHz
2
m Cl m Cl 34.9688
1000 6.022 10 23 2.903 10 26 kg
(m Cl6. The
Problem m Cl )wavenumbers
2 2of the J=0 to J=1 transitions for 1H35Cl and 2H35Cl are
20.8784 and 10.7840 cm−1, respectively.
(6.626 10 Accurate
34
J s) molar masses are 1.00782535g/mole
rCl Cl g/ mole
and 2.0140 for proton and deuterium, respectively. The molar 1.989of
mass Å Cl is
2 2 (Based
34.96885 g/mole.
10
2.9979on10thiscm s 1 )(2.903determine
information 10 26 kg)(accurate
0.9752cm 1
)
internuclear distances in
HCl and DCl. Are they the same?
h (J 1) h (1) h
4. J J 1 0 1 rH Cl
4 2 cI 4 2 cI 4 2
c 0 1

m 35 Cl m 1 H (34.9688)(1.007825)
1000 6.022 10 23 1.6267 10 27
kg
(m 35 Cl m1H ) (34.9688 1.007825)
(6.626 10 34 J s)
rH Cl 1.2839Å
4 2 (2.9979 1010 cm s 1 )(1.6267 10 27 kg)(20.8784cm 1 )

27
Similarily, 3.1623 10 kg and rD Cl 1.2813Å . This is a difference of ~ 0.2%.