Symmetry and Molecular Spectros
Symmetry and Molecular Spectros
Symmetry and
Molecular Spectroscopy
Lecture no. 7
Molecular Spectroscopy:
Rotational, vibrational and
Roto-vibrational Spectroscopy of diatomic Molecules
Giuseppe Pileio
Learning Outcomes
By the end of this lecture you will be able to:
!! Understand the fundamentals of pure rotational
spectroscopy
!! Understand the fundamentals of pure vibrational
spectroscopy of diatomic molecules
!! Understand the fundamentals of roto-vibrational
spectroscopy of diatomic molecules
!! Extract molecular information from these molecular
spectra
2
mi ""r2i "jk
$ rij "rik #
i!1
! principal frame !
Ixx 0
0
0 Iyy 0
0
0 Izz
1.! Linear
2.! Symmetric
3.! Spherical
CH4, SF6
4.! Asymmetric
H2O, NO2
NH3, CHCl3
!
!
" e.r
I~
r"
e
! !i,el " "!j,el "% el "! !i,vib "!j,vib "% vib
Group Theory:
o! If the molecule has a dipole moment it should lie on its
principal axis
o! Homonuclear diatomic molecules cannot have a
permanent dipole since the two atoms equally attract
electrons
o! Molecules with a centre of inversion cannot have a
permanent dipole
o! Spherical molecules cannot have a permanent dipole
Heteronuclear "+
diatomic
Homonuclear
diatomic
"-
Non-centrosymmetric
"+
Spherical
"-
"+
"-
"+
"+
"+
"+
Rigid Rotor
E!
I ! r2
!
J=3
6B
4B
2B
J=2
J=1
J=0
"I 2
m1 "m2
m1 % m2
# QuantumTheory
EJ ! B J"!J # 1"
B!
!2
2"I
J ! 0, 1, 2, ...
Non-rigid rotor
Restoring Force
F=-k(r-re)
re
Classical theory:
r
E!
1
2
"Ie 2 $
1 Ie 4
"
2 k
QuantumTheory
J=3
J=3
6B
J=2
4B
J=2
J=1
2B
J=1
J=0
J=0
rigid
non-rigid
!2
2"I
!4
2#I3 #k
!J " # 1
Rigid rotor
gj
gi
"e#$E!kT
nJ
n0
! !2"J # 1""e$BJ"!J#1"#kT
"+
"+
"-
"+
"-
"-
"+
"+
"+
11
q ! !r " re "
re
F ! "k q
E!
1
2
#k q2
# QuantumTheory
Ev ! v "
1
2#
#h
v ! 0, 1, 2, ...
12
QuantumTheory:
Ev ! v "
e !
1
2
#h e %
De
v"
#h e #xe
h e
xe !
2#
4#De
13
!v " # 1
"!v# 1 "$h#kT
2
" 1 $h#kT
e 2
! e"vh#kT
14
$v=1!
~2B!
$J=1!
$J=0!
~h#!
~4B!
~2B!
$v=0!
$J=2!
$J=1!
$J=0!
1
2
$e " v #
with
e "
"h e $
1
2
v#
1
2
anharmonic oscillator
"h e "xe
vibro-rotational coupling
"J"!J # 1"
3# !3 #e
2# r2e #De
1
re
1
2 #r2e
and also:
Ev,J ! Bv J"!J # 1" $ D J2 "!J # 1"2 # v #
Bv ! Be " e $ v %
1
2
1
2
"h e $
v#
1
2
"h e "xe
16
!2
2"
r2e
"
m1 #m2
17
~B0,B1
m1 $ m2
HCl
no Q band
18
19
CO
R " E#!1, J $ 1" $ E#!0, J $ 2" " h e $ !2 & !$3 & J" J" B0 & !$1 & J" J B1
P $ R " 2 !1 $ 2 J" B0
20
R " E#!1, J & 1" $ E#!0, J" " h e $ J !1 & J" B0 & !1 & J" !2 & J" B1
P $ R " $2 !1 & 2 J" B1
Bv ! Be " e $ v %
Be !
e "
!2
2" r2e
De
2%
21
1
2