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The Rigid Rotor: Diatomic Molecule
The Rigid Rotor: Diatomic Molecule
The Rigid Rotor: Diatomic Molecule
r1 + r2 r0
m1
r1 mrmr=
(center of mass)
COM r2 m2
K.E. K=
1
2
1 1
(
m1r12 2 + m2 r22 2 = m1r12 + m2 r22 2
2 2
)
I moment of inertia
1 2
K= I
2
m1 m2
I = m1r12 + m2 r22 = µ r02 µ= (reduced mass)
m1 + m2
1 2 2 1 2
K= µ r = µ v0
2 0 2
z
Problem reduced to
a one-body problem
µ
with mass µ. r0
y
x
5.61 Fall 2004 Lecture #17-19 page 2
1 2 L2
K = I =
2 2I
2 2
(
H = K + V x, y, z =
ˆ )
+ V x, y, z
2 µ xyz
( )
2 2 2
2xyz = + +
x 2 y 2 z 2
1 2 1 1 2
2
= 2 r + 2 sin + 2 2
r r r r sin
r
r sin 2
⎪⎧ ⎡ 1 ∂ ⎛ 2 ∂ ⎞ ∂ ⎛ ∂⎞ ∂2 ⎤ ⎫
2
⎨− ⎢ 2 ⎜r ⎟+ 2
1 1
⎜ sinθ ∂θ ⎟⎠ + r 2 sin2 θ ∂φ 2 ⎥ + V r,θ , φ ( )⎪⎬ψ ( r,θ ,φ )
⎪⎩ 2 µ ⎣ r ∂r ⎝ ∂r ⎠ r sin θ ∂θ ⎝ ⎦ ⎪⎭
(
= Eψ r,θ , φ )
In our rigid rotor example
( )
V r,θ , φ = 0 (r = r ) 0
i.e. r is held constant at r0.
V ( r,θ , φ ) = ∞ ( r ≠ r ) 0
(
ψ r,θ , φ ) → (
ψ r0 ,θ ,φ )
∂
∂r
( )
ψ r0 ,θ , φ = 0
2 ⎡ 1 ∂ ⎛ ∂⎞ 1 ∂2 ⎤
− ⎢ ( )
⎜ sin θ ∂θ ⎟⎠ + sin 2 θ ∂φ 2 ⎥ ψ r0 ,θ ,φ = Eψ r0 ,θ , φ ( )
2 µ r02 ⎣ sin θ ∂θ ⎝ ⎦
I
Set ( ) ( )
ψ r0 ,θ , φ = BY θ , φ
Need to solve
2 ⎡ 1 ∂ ⎛ ∂⎞ 1 ∂2 ⎤
− ⎢ ( )
⎜ sinθ ∂θ ⎟⎠ + sin 2 θ ∂φ 2 ⎥ Y θ , φ = EY θ , φ ( )
2I ⎣ sin θ ∂θ ⎝ ⎦
5.61 Fall 2004 Lecture #17-19 page 4
Solving for the rigid rotor problem, we are now left with solving the diff. eq.
2 ⎡ 1 ∂ ⎛ ∂⎞ 1 ∂2 ⎤
−
2I
⎢
sin θ ∂θ
( ) ( )
⎜⎝ sinθ ∂θ ⎟⎠ + sin 2 θ ∂φ 2 ⎥ Y θ , φ = EY θ , φ
⎣ ⎦
This is ( ) ( )
ĤY θ , φ = EY θ , φ
⎡ ∂ ⎛ ∂ ⎞ 2IE 2 ⎤ ∂2
⎢sinθ
∂θ
( )
⎜⎝ sinθ ∂θ ⎟⎠ + 2 sin θ ⎥ Y θ ,φ = − ∂φ 2 Y θ , φ( )
⎣ ⎦
only θ only φ
∴ Try ( ) () ()
Y θ ,φ = Θ θ Φ φ as a solution
2IE
Define β≡
2
( note β ∝ E )
⎡ ∂ ⎛ ∂⎞ ⎤ ∂2
⎢sinθ
∂θ
() ()
⎜⎝ sinθ ∂θ ⎟⎠ + β sin θ ⎥ Θ θ Φ φ = − ∂φ 2 Θ θ Φ φ
2
() ()
⎣ ⎦
Since and are independent variables, each side of the equation must be
equal to a constant m2.
2
1
= m2 () I
()
2
sin
and sin + sin 2 = m2 () II
()
( ) = m
2
2 () 2
()
Solutions are = Am e
im
and A m e im
(
+ 2 = ) ()
(
im + 2 ) (
im + 2 )
Am e = Am eim and A m e = A m e im
( )
im 2 ( )
im 2
e = 1 and e =1
()
= Am eim m = 0, ± 1, ± 2, ± 3,....
() ()
2
Normalization:
0
d = 1
5.61 Fall 2004 Lecture #17-19 page 6
=() 1
eim m = 0, ± 1, ± 2, ± 3,...
2
()
Now let’s look at . Need to solve II
sin
sin ()
+ sin2 = m2
()
Since 0 1 x +1
m2
(1 x )
2 d2
dx 2
() d
P x 2x P x +
dx
()
2
P x =0 ()
1 x
(
= l l +1 ) where l = 0, 1, 2,...
and m = 0, ± 1, ± 2,..., ±l
2 IE 2
= 2 E=
2I
2
E=
2I
(
l l +1 ) l = 0, 1, 2,... (for rigid rotor, use J instead of l)
2
EJ =
2I
J J +1 ( ) J = 0, 1, 2,...
5.61 Fall 2004 Lecture #17-19 page 7
m
Solutions of Legendre eq. are associated Legendre polynomials Pl
Pl
m
( x ) = P (cos )
l
m
( ) P ( cos ) = ( 3cos 1)
1
P00 cos = 1 2
0 2
2
P ( cos ) = cos
1
0
P (cos ) = 3cos sin
2
1
P ( cos ) = sin
1
1
P ( cos ) = 3sin
2
2 2
etc.
()
So = Alm Pl
m
(cos )
2l + 1
Alm =
( l m )! 2
2 ( l + m )!
where Alm is the normalization constant
2
( )
Alm2 Pl cos sin d = 1
m
0
( ) ( )
lm r0 , , = Yl m , = l m
m
() ()
1
Yl m
( )
2l + 1
, =
( l m )! 2
Pl
m
(cos ) e im
4 ( l + m )!
These functions are called spherical harmonics.
1
1 3 2
Y00 = Y11 = sin ei
( 4 ) 8
12
1 1
3 2 3 2
Y10 = cos Y11 = sin e i
4 8
etc.
SPHERICAL HARMONICS
( ) m
Yl m , = l m () ()
1
Yl m
( )
2l + 1
, =
( l m )! 2
Pl
m
(cos ) e im
4 ( l + m )!
l = 0, 1, 2,... m = 0, ± 1, ± 2, ± 3,... ± l
( 4 ) 16
12
1 1
3 2 15 2
Y10 = cos Y2±1 = sin cos e±i
4 8
1 1
3 2 15 2 2 ±2i
Y11 = sin ei Y2±2 = sin e
8 32
1
3 2
Y11 = sin e i
8
1 if l = l 1 if m = m normalization
Krönecker delta ll = mm =
0 if l l 0 if m m orthogonality
5.61 Fall 2004 Lecture #17-19 page 9
Energies: ˆ m = E Ym)
(eigenvalues of HYl lm l
Switch l J conventional for molecular rotational quantum #
Recall
2 IE
(
= 2 = l l +1 J J +1
) (
J = 0, 1, 2,... )
2
EJ =
2I
J J +1 ( )
J=2
2
J=1 E1 =
I
(
Y10 , Y1±1 3x degenerate )
J=0 E0 = 0 (
Y00 nondegenerate )
Degeneracy of each state (
g J = 2J + 1 )
from m = 0, ± 1, ± 2,..., ± J
2 2
E J +1 E J = ( )(
J +1 J + 2 J J +1 =
2I
)
I J +1 ( ) ( )
Transitions between rotational states can be observed through
spectroscopy, i.e. through absorption or emission of a photon
+ +
h Absorption
EJ EJ+1
- -
+ +
or Emission h
EJ EJ-1
- -
5.61 Fall 2004 Lecture #17-19 page 10
2
dµ
( )
Strength of transition I JJ J µ J dx
dx
(
J J +1 (Hz) = 2 B J + 1 ) (
J J +1 (cm -1 ) = 2B J + 1 )
E
J=3 E3 = 12 Bhc
E2 3 = 6Bhc
J=2 E2 = 6Bhc
E12 = 4Bhc
J=1 E1 = 2 Bhc
E01 = 2 Bhc
5.61 Fall 2004 Lecture #17-19 page 11
This gives rise to a rigid rotor absorption spectrum with evenly spaced lines.
2B
( ) (
J +1 J + 2 J J +1 = 2 B J + 1 + 1 2B J + 1 = 2B )
Use this to get microscopic structure of diatomic molecules directly from
the absorption spectrum!
h m1 m2
2B = I = µ r02 µ=
4 2 cI m1 + m2
1 1
h 2 h 2
r0 = 2 -1
(B in cm ) or r0 = 2 (B in Hz)
8 cB µ 8 B µ