Rotational Motion 2009 7

18_12afig_PChem.
jpg
Rotational Motion
Center of Mass
Translational Motion
r
1
r
2
2

2
H
m
= V V
2

2
H
I
= L L
2
2

( )
2 2
eq
k
H
= V V+ r r
Motion of Two Bodies
Each type of motion is best represented
in its own coordinate system best suited
to solving the equations involved
e
k
2 2
2 2
1 2 1 2
1 2

( , )
2 2
H V
m m
= V V + r r
R
c

Internal
coordinates
Cartesian
Internal motion (w.r.t CM)
Motion of the C.M.
2
'
r
1
'
r
Origin
r
Vibrational Motion
Centre of Mass
( ) ( ) ( )
1 1 2 2
1 1 1 1 2 2 2 2
1 2
, , , , , ,
m m
X Y Z x y z x y z
m m
+
= = = =
+
r r
R r r
Weighted average of all positions
1 1 2 2
1 2
m x m x
X
m m
+
=
+
1 1 2 2
1 2
m y m y
Y
m m
+
=
+
1 1 2 2
1 2
m z m z
Z
m m
+
=
+
2 2
2 2

( ) ( ) ( )
2 2
H H H V
M
= + = V V +
R r
R r r
Motion of Two Bodies
Internal Coordinates:
1 1 2 2
&
' '
= + = + r r R r r R
1 2
= r r r
( )
1 2 1 2
' ' ' '
= + + = r r R r R r r
In C.M. Coordinates:
( , , ) x y z = r
Kinetic Energy Terms
2 2
2 2

( ) ( )
2 2
K K K
M
= + = V V
R r
R r
?
?
2 2 2 2 2
2
2 2 2

( )
2 2
d d d
K
M M dX dY dZ
(
= V = + +
(

R
R
2 2 2 2 2
2
2 2 2

( )
2 2
d d d
K
dx dy dz
(
= V = + +
(

r
r
? ? ?
? ? ?
Centre of Mass Coordinates
1 1 1
d dX d dx d
dx dx dX dx dx
= +
1 1 2 2 1 1
1 1 1 2 1 2
m x m x m m dX d
dx dx m m m m M
(
+
= = =
(
+ +

| |
1 2
1 1
1
dx d
x x
dx dx
= =
1
1
m d d d
dx M dX dx
= +
2 2 2
d dX d dx d
dx dx dX dx dx
= +
1 1 2 2 2 2
2 2 1 2 1 2
m x m x m m dX d
dx dx m m m m M
(
+
= = =
(
+ +

| |
1 2
2 2
1
dx d
x x
dx dx
= =
2
2
m d d d
dx M dX dx
=
2
1 1
2
1
m m d d d d d
dx M dX dx M dX dx
( (
= + +
( (

2 2 2
1 1 1
2 2 2
m m m d d d d d d
M dX M dX dx dx M dX dx
= + + +
2 2 2 2
2 2
2 2 2 2
2
2 m m d d d d
dx M dX M dXdx dx
= +
Similarly
2 2 2
1 1
2 2 2
2 m m d d d
M dX M dXdx dx
= + +
2 2 2
1
2 2 2 2
1 1 1
1 2 1 m d d d d
m dx M dX M dXdx m dx
= + +
2 2 2 2 2 2
1 2
2 2
1 2 1 1 2 2
1 1
2 2
x x
x
d d
K
m m m dx m dx
( (
V V
= + = +
( (

2 2 2
2
2 2 2 2
2 2 2
1 2 1 m d d d d
m dx M dX M dXdx m dx
= +
2 2 2 2 2 2
1 2
2 2 2 2 2 2 2 2
1 1 2 2 2 1
1 1 1 1 m m d d d d d d
m dx m dx M dX M dX m dx m dx
+ = + + +
2 2 2 2
1 2
2 2 2 2 2 2
1 1 2 2 1 2
1 1 1 1 m m d d d d
m dx m dx M M dX m m dx
( (
+ = + + +
( (

2 2
2 2
1 1 d d
M dX dx
= +
1 2
1 2 1 2
1 1 1 mm
m m m m
= + =
+
Reduced mass
2 2 2
2 2
1 1
2
x
d d
K
M dX dx
(
= +
(

2
2 2
internal
1 1

2
CM
K K K
M
(
= V + V = +
(

R r
2 2 2
2
2 2 2
d d d
dX dY dZ
V = + +
R
2 2 2
2
2 2 2
d d d
dx dy dz
V = + +
r
Hamiltonian
2 2
2 2

( ) ( ) ( )
2 2
H H H V
M
= + = V V +
R r
R r r
| |

( , ) ( ) ( ) ( ) ( ) ( ) ( ) H H H E E
(
+ = + = +

R r
R r R r R r R r
( ) ( ) ( ) H E =
R
R R R
2
2

( ) ( ) ( )
2
V E
= V + =
r r
r r r
2
2
( ) ( )
2
E
M
= V =
R R
R R
( ) ( ) ( ) H E =
r
r r r
C.M. Motion
3-D P.I.B
Internal Motion
Rotation
Vibration
Separable!
Rotational Motion and Angular Momentum
2
2
( ) ( )
2
K
= V
r
r r
We rotational motion to internal coordinates
i i
i
p mv =
Linear momentum of a rotating Body

i i
i
p m re
'
=
i i
d
v r
dt
u
'
=
As
i
s r u
'
A = A
i
ds
v
dt
=
i i
v re
'
=
d
dt
u
e =
|
Angular Velocity
Parallel to moving body
p(t
1
)
p(t
2
)
Always changing direction with time???
Always perpendicular to r
Angular Momentum
= L r p
v
m
r
e
p
L
= L r p
|
sin| = r p = r p
Perpendicular to R and p
Orientation remains constant with time
i i
i
'
=
L r p
Ie = L
2
i i
i
m e
'
=
r
2
i i
i
m e
(
'
=
(

r
2
i i
i
I m
'
=
r
Moment of inertia
As p is always perpendicular to r
2
' ' ' ' '
= = r r r r r
r
Center
of mass
R
1
'
r
2
'
r
1 2 1 2
' '
= = r r r r r
2 2
1 1 2 2
I m m
' '
= + r r
r
Center
of mass
R
1
'
r
2
'
r
2 2
1 1 2 2
m m = + r R r R
| |
2 2
1 2
m m
M M
= = r r r
| |
| |
1 1 2 2
1 1 1 1 2 1 1 1 2 2
1
m m
M
m m m m
M M M
+
= = +
r r
r R r r r r r
2
2
1 2
1 2
1 1 m m
m m M
(
| |
= +
( |
\ .

r
( )
2 2 2 1

(
= =
(

r r
| |
1 1
2 2 1
m m
M M
= = r R r r r
2 2
2 2
2 1
1 2
m m
I m m
M M
| | | |
= +
| |
\ . \ .
r r
Classical Kinetic Energy
2
. .
2
i
i
i
p
K E
m
=
( )
2
2
2 2
i i
i i
i i
m r
m v
e
'
= =

( )
2 2
2
2 2 2
L I
I
I I
e
e
= = =
2 2
2 2
2 2
i i
i
m r
e e
(
'
= =
(

r
r
Center
of mass
R
1
'
r
2
'
r
2
. .
2
L
K E
I
=
2
1

2
K L
I
=
2
2
2
K
= V
r
2
( ) ( )
2
L
K
I
= r r
2
2
( ) ( )
2
K
= V
r
r r
L i r = V
r
( ) ( )
2
= V V
r r
r r
Since r and p are
perpendicular
r
Center
of mass
R
1
'
r
2
'
r
( )
( )
2 2
2 2 2 2
I
L

= V = V = V V
r r r r
r r
r r
Momentum Summary
( )
2 1
2
K r p
I
=
2
2
2
K
= V
L i r = V
Linear
Classical QM
Rotational
(Angular)
Momentum
Energy
Momentum
Energy ( )
2
2
2
K r
I
= V
p i = V
L r p =
dr
p mv m
dt
= =
2 2
2
2 2
p m d r
K
m dt
= =
Angular Momentum
= L r p
| |
x y z
x y z p p p
(
=

L
x y z
x y z
p p p
=
i j k
L
Angular Momentum
x y z
L L L = + + L i j k
x z y
y x z
z y x
L yp zp
L zp xp
L xp yp
=
=
=
Angular Momentum in QM
| |
( ) ( )
( ) ( )

( ) ( )
x x z y
y y x z
z z y x
L L yp zp
L L zp xp
L L xp yp

( = =

= =
( = =

r r
r r
r r
x
y
z
d d
L i y z
dz dy
d d
L i z x
dx dz
d d
L i x y
dy dx
(
=
(

(
=
(

(
=
(

x y z
L L L = + + L i j k
Angular Momentum

i = = V L r p r
| |
d d d
x y z i
dx dy dz
(
=
(

L
i x y z
d d d
dx dy dz
=
i j k
L
Angular Momentum
x y z
L L L = + + L i j k
x
y
z
d d
L i y z
dz dy
d d
L i z x
dx dz
d d
L i x y
dy dx
(
=
(

(
=
(

(
=
(

Two-Dimensional Rotational Motion
cos( ) x r | =
x
y
|
r
sin( ) y r | =
d d
dx dy
(
V = +
(

i j
How to we get:
( , ) ( , )
d d
r r
dx dy
| |
(
V = +
(

i j
Polar Coordinates
cos( ) sin( )
d dx d dy d d d
dr dr dx dr dy dx dy
| | = + = +
sin( ) cos( )
d dx d dy d d d
r r
d d dx d dy dx dy
| |
| | |
= + = +
2 2
2
2 2
d d
dx dy
(
V = +
(

2 2
2
2 2
( , ) ( , )
d d
r r
dx dy
| |
(
V = +
(

cos( ) sin( )
d dx d dy d d d
dr dr dx dr dy dx dy
| | = + = +
d d d
r x y
dr dx dy
= +
2 2
1 d x d y d
r dr r dx r dy
= +
2 2
1 d d x d y d d d
r x y
r dr dr r dx r dy dx dy
( (
= + +
( (

2 2 2 2
x d d x d d y d d y d d
x y x y
r dx dx r dx dy r dy dx r dy dy
= + + +
2 2 2 2
2 2 2 2 2 2 2 2
x d x d xy d yx d y d y d
r dx r dx r dxdy r dydx r dy r dy
= + + + + +
2 2 2 2
xx d d xy d d yx d d y dy d d d
y
r dx dx r dx dy r dy dx r dy dy dy dy
(
= + + + +
(

product rule
sin( ) cos( )
d dx d dy d d d d d
r r y x
d d dx d dy dx dy dx dy
| |
| | |
= + = + = +
2
2
d d d d d
y x y x
d dx dy dx dy |
( (
= + +
( (

2 2
2 2
2 2
d dx d d d d d d d
y y yx x xy x
dx dx dy dx dy dx dy dx dy
= +
d d d d d d d d
y y y x x y x x
dx dx dx dy dy dx dy dy
(
= + +
(

2 2 2 2 2
2 2 2 2 2 2 2 2 2 2
1 d y d y d yx d x d xy d x d
r d r dx r dy r dxdy r dx r dydx r dy |
= +
2 2
2 2
2 2
d d d d d d
y y yx x xy x
dx dy dxdy dx dydx dy
= +
product rule
2 2 2 2
2 2 2 2 2 2 2 2
1 d d x d x d xy d yx d y d y d
r
r dr dr r dx r dx r dxdy r dydx r dy r dy
= + + + + +
2 2 2 2 2
2 2 2 2 2 2 2 2 2 2
1 d y d x d yx d xy d y d x d
r d r dx r dx r dxdy r dydx r dy r dy |
= +
2 2 2 2 2 2 2 2 2
2 2 2 2 2 2 2 2 2 2
1 1 d d d x d y d x d y d
r
r dr dr r d r dx r dx r dy r dy |
+ = + + +
2 2 2 2 2 2
2 2 2 2 2 2
x y d x y d
r r dx r r dy
( (
= + + +
( (

2 2
2
2 2
d d
dx dy
= + = V
2
2
2 2
1 1 d d d
r
dr r dr r d|
V = +
2 2 2
2 2 2 2
1 1 d d d d d
r
dr r dr r d dx dy |
+ = +
2 2 2
2
2 2
1 1
2 2
d d d
H r
dr r dr r d |
(
= V = +
(

Two-Dimensional Rigid Rotor
2
2
( , ) ( , ) ( , )
2
H r r E r | | |
= V =
Assume r is rigid, ie. it is constant
2 2 2
2
2 2
1 1
2 2
d d d
H r
dr r dr r d |
(
= V = +
(

2 2 2
2
2 2
1
2 2
r
d
H
r d |
= V =
2
2
z
L
H
I
=

z r
d
L i i
d|
= V =
As the system is rotating about the z-axis
18_05fig_PChem.jpg
2 2
2
( ) 0
2
d
E
I d
|
|
(
=
(

2
2 2
2
( ) 0
d I
E
d
|
|
(
+ =
(

2
2
2
( ) 0
d
k
d

|
(
+ =
(

r
2 2
2
2
2
2
I k
k E
I
= =
2 2
2
( ) ( ) ( )
2
d
H E
I d
| | |
|
= =
18_05fig_PChem.jpg
2
2
2
( ) 0
d
k
d
|
|
(
+ =
(

( ) 0
d d
ik ik
d d
|
| |
( (
+ =
( (

( ) 0 & ( ) 0
d d
ik ik
d d
| |
| |
( (
+ = =
( (

( )
ik
A e
|
|
+ +
=
( )
ik
A e
|
|

=
18_05fig_PChem.jpg
( )
ik
A e
|
|
+ +
=
Periodic
2 2 2 2
2 2
m
k m
E E
I I
= = =
( ) 2
( 2 ) ( )
ik
ik
A e A e
| t
|
| t |
+
+ + + +
+ = = =
( ) 2
1 2 2
ik
e k m k m k
t
t t = = = e
m = quantum number
( )
im
m
A e
|
|
+ +
=
( )
im
m
A e
|
|

=
18_05fig_PChem.jpg
( )
im
m
A e
|
|

=
2 2 2
2
2
2 2
r
d
H
I d |
= V =
z r
d
L i i
d|
= V =
2 2
( ) ( )
2
m m
m
H
I
| |

=
2 2
2
m
m
E
I
=
( ) ( )
z m m
L m | |

=
2
2 2
2
d
L
d|
=
2 2 2
( ) ( )
m m
L m | |

=
zm
L m =
2 2 2
m
L m =
( )
im
m
A e
|
|

=
( ) ( )
m m
H E | |
=
2 2
2
m
m
E
I
=
( ) ( )
z m m
L m | |

=
zm
L m =
E
m
zm
L
m
E
m
2
I
| |
|
\ .
18.0
12.5
8.0
4.5
2.0
0.5
6
5
4
3
2
6
5
4
3
2
1
Only 1 quantum number is require to determine the state of the system.
Normalization
( )
im
m
A e
|
|
+ +
=
| | | |
2 2
* *
0 0
( ) ( ) 1 & ( ) ( ) 1
m m m m
t t
| | | |
+ +
= =
} }
| |
*
*
*
( )
im im
m
A e A e
| |
|

+ + +
(
= =

( )
im
m
A e
|
|

=
*
A A
+

=
| |
*
( ) ( )
m m
| |
+
=
Normalization
| |
2 2
*
0 0
1 ( ) ( ) ( ) ( )
m m m m
d d
t t
| | | | | |
+ + +
= = =
} }
2 2 2
2 2
0 0 0
1 1 [2 ]
im im im im
A A e e d A A e e d A d A
t t t
| | | |
| | | t
+
+ +
= = = =
} } }
1
2
A
t
=
1
( )
2
im
m
e
|
|
t
+
=
1
( )
2
im
m
e
|
|
t

=
| |
2 2
*
0 0
( ) ( ) ( ) ( ) 1
m m m m
d
t t
| | | | |
+
= =
} }
18_06fig_PChem.jpg
1
( )
2
im
m
e
|
|
t
=
Orthogonality
| |
2
*
,
0
( ) ( )
m m m m
d
t
| | | o
' '
=
}
*
2
0
1 1
2 2
im im
e e d
t
| |
|
t t
'
(
=
(

}
2
0
1
2
im im
e e d
t
| |
|
t
'
}
m = m 2
0
1 2
1 1
2 2
d
t
t
|
t t
= = =
}
m m
( )
( ) ( )
2 2
0 0
1 1
cos( ) sin( )
2 2
i m m
e d m m i m m d
t t
|
| | | |
t t
'
' '
= = +
} }
( ) ( )
2 2
0 0
1
cos( ) sin( )
2 2
i
m m d m m d
t t
| | | |
t t
' '
= +
} }
1
0 0 0
2 2
i
t t
= + =
14_01fig_PChem.jpg
x y z = + + r i j k
sin cos sin sin cos r r r u | u | u = + + r i j k
Spherical Polar Coordinates
d d d
dx dy dz
V = + + i j k
( , , ) ( , , ) ( , , )
d d d
r r r
dx dy dz
u | u | u |
(
V = + +
(

i j k
( , , ) ( , , )
( , , )
x r y r
z r
u | u |
u |
= +
+
r i j
k
?
14_01fig_PChem.jpg
sin cos sin sin cos x r y r z r u | u | u = = =
d dx d dy d dz d
dr dr dx dr dy dr dz
= + +
cos sin sin sin cos
d d d d
dr dx dy dz
| u | u u = + +
cos cos sin cos sin
d d d d
r r r
d dx dy dz
| u | u u
u
= +
sin sin cos sin
d d d
r r
d dx dy
| u | u
|
= +
.... & ....
d d
d d u |
= =
14_01fig_PChem.jpg
The Gradient in Spherical Polar Coordinates
cos sin sin sin cos
cos cos sin cos sin
sin sin cos sin 0
d d
dr dx
d d
r r r
d dy
r r
d
d
d
dz
| u | u u
| u | u u
u
| u | u
|
( (
( (
( ( (
( ( (
=
( ( (
( ( (

( (
( (

. SP Cart
V = V W
Gradient in Spherical Polar
coordinates expressed in
Cartesian Coordinates
14_01fig_PChem.jpg
cos cos sin
cos sin
sin
sin cos cos
sin sin
sin
sin
cos 0
Cart
d d
dx r r dr
d d
dy r r d
d
d
r d
dz
| u |
| u
u
| u |
| u
u u
u
u
|
( (
(
( (
(
( (
(
( (
(
V = =
( (
(
( (
(
( (
(
( ( (

1
. Cart SP
V = V W
Gradient in Cartesian
coordinates expressed in
14_01fig_PChem.jpg
1
.
cos cos sin
cos sin
sin
sin cos cos
sin sin
sin
sin
cos
Cart SP
d d d
d
dr r d r d
dx
d d d d
dy dr r d r d
d d d
dr r d dz
| u |
| u
u u |
| u |
| u
u u |
u
u
u
(
(
+
(
(
(
(
(
(
V = = + + = V
(
(
(
(
(
(

(
(

W
.
Cart
i = V L r
1
SP
i

= V L r W
14_01fig_PChem.jpg
cos cos sin
cos sin
sin
cos( )sin( )
sin cos cos
sin( )sin( ) sin sin
sin
cos( )
sin
cos
d d d
dr r d r d
r
d d d
i r
dr r d r d
r
d d
dr r d
| u |
| u
u u |
| u
| u |
| u | u
u u |
u
u
u
u
(
+
(
( (
( (
+ +
( (
( (

(
(

x y z
L L L = + + L i j k
cos
sin cos
sin
cos
cos sin
sin
x
y
z
d d
L i
d d
d d
L i
d d
d
L i
d
u
| |
u u |
u
| |
u u |
|
(
=
(

(
=
(

=
i = V = L r
14_01fig_PChem.jpg
The Laplacian in Spherical Polar Coordinates
2
2 2
2 2 2 2 2
1 1 1
sin
sin sin
d d d d d
r
r dr dr r d d r d
u
u u u u |
V = + +
2
2
2
1
.....
d
r
r dr
V = + OR
OR
2
2
2
2
....
d d
dr r dr
V = + +
Radial Term
Angular Terms
2 1 1
Cart SP SP

( (
V = V V

W W
Three-Dimensional Rigid Rotor
Assume r is rigid, ie. it is constant. Then all energy is from rotational motion only.
2 2 2 2 2
2
.
2 2 2
2 2
Cart
d d d
H
dx dy dz
(
= V = + +
(

2 2 2
2
2 2 2 2
1 1 1
sin
2 2 sin sin
SP
d d d d d
H r
r dr dr r d d r d
u
u u u u |
(
= V = + +
(

2 2
2 2 2
1 1
sin
2 sin sin
d d d
H
r d d d
u
u u u u |
(
= +
(

2
2I
=
L
2
2 2
2 2
1 1
sin
sin sin
d d d
L
d d d
u
u u u u |
(
= +
(

18_05fig_PChem.jpg
2 2
2 2
1 1
( , ) sin ( , ) ( , )
2 sin sin
d d d
H E
I d d d
u | u u | u |
u u u u |
(
= + =
(

2 2
2 2
1 1
sin ( ) ( ) ( ) ( )
2 sin sin
d d d
E
I d d d
u u | u |
u u u u |
(
+ O u = O u
(

2
2
2
sin sin ( ) ( ) ( ) ( ) sin ( ) ( )
d d d
d d d
u u u | u | | u u |
u u |
O u + O u = O u
2
2
2
2
IE
E
I
| | = =
Separable?
2
2
2
1
( )
( )
d
k
d
|
| |
u =
u
2 2
1
sin sin ( ) sin
( )
d d
k
d d
u u u | u
u u u
O + =
O
2
2
2
( )sin sin ( ) ( ) ( ) sin ( ) ( )
d d d
d d d
| u u u u | | u u |
u u |
u O + O u = O u
2
2
2
1 1
sin sin ( ) sin ( )
( ) ( )
d d d
d d d
u u u | u |
u u u | |
O + = u
O u
Two separate
independent
equations
k
2
= separation
Constant
18_05fig_PChem.jpg
2
2
2
( ) 0
d
k
d
|
|
(
+ u =
(

1
( )
2
im
m
e
|
|
t
+
u =
1
( )
2
im
m
e
|
|
t

u =
k m k = e
2
2
2
1
( )
( )
d
k
d
|
| |
u =
u
Recall 2D Rigid Rotor
18_05fig_PChem.jpg
2 2
1
sin sin ( ) sin
( )
d d
m
d d
u u u | u
u u u
O + =
O
2 2
sin sin sin ( ) ( )
d d
m
d d
u u | u u u
u u
(
+ O = O
(

( )
,
( ) cos( )
m
m
l m l l
C P u u O =
This equation can be solving using a series expansion, using a Fourier Series:
Where
( 1) l l | = +
2
2
( 1)
2 2
l
l l
E E
I I
|
+
= = =
Legendre polynomials
2 2
sin sin ( ) sin ( ) ( )
d d
m
d d
u u u | u u u
u u
O + O = O
2
( 1)
2
l
l l
E
I
+
=
2 2
2 2
1 1
sin ( , ) ( , )
2 sin sin
d d d
E
I d d d
u u | u |
u u u u |
(
+ =
(

1
( )
2
im
m
e
|
|
t
u =
, ,
( ) ( ) ( ) ( )
l m m l l m m
H E u | u | O u = O u
,
( ) (cos( ))
m m
l m l l
C P u u O =
2
1 ( 1) 1
(cos( )) (cos( ))
2
2 2
m m
m im m im
l l l l
l l
H C P e C P e
I
| |
u u
t t
+ ( (
=
( (

,
1
( , ) (cos( ))
2
m
m im
l m l l
Y C P e
|
u | u
t
=
Spherical Harmonics
, ,
( , ) ( , )
l m l l m
HY EY u | u | =
The Spherical Harmonics
,
1
( , ) (cos( ))
2
m
m im
l m l l
Y C P e
|
u | u
t
=
, 1,..., 1, m l l l l = + + +
1/2
(2 1)( )!
for 0
2( )!
m
l
l l m
C m
l m
(
+
= <
(
+

1/2
(2 1)( )!
( 1) for 0
2( )!
m m
l
l l m
C m
l m
(
+
= >
(
+

For l=0, m=0
2
1
(cos ) (cos 1)
2 ! (cos )
l
l
l
l
d
P
l d
u u
u
(
=
(

(cos ) sin (cos )
(cos )
m
m m
l l
d
P P
d
u u u
u
(
=
(

0
2 0
0
1
(cos ) (cos 1) 1
2 0! (cos )
l
d
P
d
u u
u
(
= =
(

0
0 0
0
(cos ) sin 1 1
(cos )
d
P
d
u u
u
(
= =
(

,
1
( , ) (cos( ))
2
m
m im
l m l l
Y C P e
|
u | u
t
=
0
0
(cos( )) 1 P u =
0
0,0
1 1 1
( , ) (1)
2 2 2
i
Y e u |
t t
= = e
For l=0, m=0
1/2
0
(2*0 1)(0 0)! 1
( 1)
2(0)!
2
m
l
C
( +
= =
(

0,0
1
, (0, ), (0, 2 )
2
o
Y r r u t | t
t
= = = =
Everywhere on the surface of the
sphere has value
1
2 t
what is r
o
? r = (r
o
, u, |)
r = (1, u, |)
Normalization:
( )
*
0,0 0,0
S
Y Y dV =
}
2
sin( ) sin( )
o
dV dxdydz
r d d d d u u | u u |
=
= =
* ( ) ( , )
( ) ( , )
1 1
1
2 2
f o f j f f f
i o i i i i i
x r y f x z g x y
x r y f x y g x y
dxdydz
t t
= = =
= = =
| |
=
|
\ .
} } }
2 2 2 2
Where
o
x y z r + + =
*
2
0 0
1 1
sin( )
2 2
d d
t t
u u |
t t
| |
=
|
\ .
} }
In Spherical Polar Coordinates
2
0 0
1
sin( )
4
d d
t t
u u |
t
=
} }
2
0 0
1
sin
4
d d
t t
u u |
t
=
} }
| | | |
2
0 0
1 1
cos 2(2 ) 1
4 4
t t
u | t
t t
= =
1
o
r =
r is fixed at r
o.

The wavefunction is an angular
function which has a constant value
over the entire unit circle.
X
Y
Z
1
2 t
( )
0
1,0
1 3 3
( , ) 1 cos( ) cos( )
2
2 2
i
Y e
|
u | u u
t t
= =
1,0
3
( ) cos( )
2
(0, ), (0, 2 )
Y u u
t
u t | t
=
= =
r = (1, u, |)
X
Y
Z
The wavefunction is an angular
function which has a value varying as
on the entire unit circle.
3
cos( )
2
u
t
The spherical Harmonics

are often plotted as a
vector strating from the
origin with orientation u
and | and its length is
Y(u,|)
Along z-axis
2 1
1
1
1
(cos ) (cos 1) cos
21! (cos )
d
P
d
u u u
u
(
= =
(

0
0 0
1
(cos ) sin cos cos
(cos )
d
P
d
u u u u
u
(
= =
(

For l=1, m=0
18_05fig_PChem.jpg
1, 1
3
( , ) sin( )
2 2
i
Y e
|
u | u
t

=
Complex Valued??
1, 1 1, 1
1 3 3
( , ) ( , ) sin( ) sin( )cos( )
2
4 2 2 2
i i
Y Y e e
| |
u | u | u u |
t t
+
+
( ( + = + = e

Along x-axis
1, 1 1, 1
1 3 3
( , ) ( , ) sin( ) sin( )sin( )
2
4 2 2 2
i i
Y Y e e
i
i
| |
u | u | u u |
t t
+
+
( ( + = + = e

Along y-axis
1
1 1
1 1
(cos ) sin (cos ) sin cos sin
(cos ) (cos )
d d
P P
d d
u u u u u u
u u
(
= = =
(

For l=1, m =1
18_05fig_PChem.jpg
( )
0 2
2
1
(cos( )) 3cos ( ) 1
2
P u u =
1
2
(cos( )) 3sin( )cos ( ) P u u u =
2 2
2
(cos( )) 3sin ( ) P u u =
2
2,0
5
( , ) (3cos ( ) 1)
4
Y u | u
t
=
2, 1
15
( , ) sin cos
2 2
i
Y e
|
u | u u
t

=
2, 1 2, 1
15
sin cos cos
2 8
Y Y
u | u
t
+
+
=
2, 1 2, 1
15
sin sin cos
2 8
Y Y
i
u | u
t
+
=
YZ XZ
2 2
2, 2
15
( , ) sin
4 2
i
Y e
|
u | u
t

=
The Spherical Harmonics Are Orthonormal
( ) ( )
2
*
, , , , ,
0 0
sin( )
l m l m l m l m
Y Y d d
t t
u u | o
' ' ' '
=
} }
2
0 0
1 1
(cos ) (cos ) sin
2 2
m m m im m im
l l l l
C P e C P e d d
t t
| |
u u u u |
t t
' ' '
' '
} }
2
0 0
1
(cos ) (cos ) sin
2
m m im im m m
l l l l
e e d C P C P d
t t
| |
| u u u u
t
' ' '
' '
=
} }
2
,
0
(cos ) (cos ) sin
2
m m
m m
l l
m m l l
C C
P P d
t
o u u u u
t
'
'
'
' '
=
}
2
,
0
When (cos ) (cos ) sin
2
m m
m m
l l
l l l l
C C
m m P P d
t
u u u u o
t
'
'
'
' '
' = =
}
Example
0
1
(cos( )) cos( ) P u u =
0
0
(cos( )) 1 P u =
2 2 0 1 0 1
0 0
0 1 1 1
0 1
0 0
(cos ) (cos ) sin cos sin 0
2 2
C C C C
P P d d
t t
u u u u u u u
t t
= =
} }
Y
l,m
are Eigenfuncions of H, L
2
, L
z

,
1
( , ) (cos( ))
2
m
m im
l m l l
Y C P e
|
u | u
t
=
2 2
2 2
1 1
sin
2 sin sin
d d d
H
I d d d
u
u u u u |
(
= +
(

2
2 2
2 2
1 1
sin
sin sin
d d d
L
d d d
u
u u u u |
(
= +
(

z
d
L i
d|
=
2
, ,
( , ) ( 1) ( , )
2
l m l m
HY l l Y
I
u | u | = +
2 2
, ,
( , ) ( 1) ( , )
l m l m
L Y l l Y u | u | = +
, ,
( , ) ( , )
z l m l m
L Y m Y u | u | =
2
( 1)
2
l
E l l
I
= +
2 2
( 1)
l
L l l = +
( 1)
l
L l l = +
z
L m =
Dirac Notation
*
, i j i j
S
ds o + + =
}
*
, i j i j
o = v v
,
N
i i m m
m
c | + =
{ }
m
|
is complete
*
, m m m m
S
| | o
' '
=
}
* * * *
,1 ,2 , 1 , i i i i N i N
c c c c
( =

v
,1
,2
, 1
,
j
j
j
j N
j N
c
c
c
c

(
(
(
(
=
(
(
(

v
Continuous Functions
Vectors
*
,
|
i j i j i j
S
ds o + + = + + =
}
i i
+ = v
Dirac
j j
+ = v
*

i j i j i j
S
ds = + + = + + = + +
}
O O O O
Bra
Ket
|
j j j
H E + = +
Dirac Notation
2
*
1,1 1,1 1,1 1,1
0 0

( , ) ( , )sin | | H Y HY d d Y H Y
t t
u | u | u u | = =
} }
1,1 1,1
| Y HY =
2 2 2
1,1 1,1 1,1 1,1 1,1
1(1 1) |
2
HY Y Y Y Y
I I I
= + = =
2 2
1,1 1,1
| Y Y
I I
= =
2
, ,
( , ) ( 1) ( , )
2
l m l m
HY l l Y
I
u | u | = +
2
1,1 1,1 1,0 1,0 1, 1 1, 1

| | | | | | Y H Y Y H Y Y H Y
I

= = =
Degenerate
Dirac Notation
2
2 * 2 2
1,1 1,1 1,1 1,1
0 0

( , ) ( , )sin | | L Y L Y d d Y L Y
t t
u | u | u u | = =
} }
2
1,1 1,1
| Y L Y =
2 2 2 2
1,1 1,1 1,1 1,1 1,1
1(1 1) 2 | 2 L Y Y Y Y Y = + = =
2 2
1,1 1,1
2 | 2 Y Y = =
2 2
, ,
( , ) ( 1) ( , )
l m l m
L Y l l Y u | u | = +
2 L =
2 2
1, 1 1, 1
| 2 Y L Y

=
2
2, 1 1, 1
| ? Y L Y

=
2 2
2, 1 2, 1
| 2 Y L Y

=
Dirac Notation
2
*
1,1 1,1 1,1 1,1
0 0

( , ) ( , )sin | |
z z z
L Y L Y d d Y L Y
t t
u | u | u u | = =
} }
1,1 1,1
|
z
Y L Y =
1,1 1,1 1,1 1,1
|
z
L Y Y Y Y = =
, ,
( , ) ( , )
z l m l m
L Y m Y u | u | =
1,1 1,1
| Y Y = =
1,0 1,0
| | 0
z
Y L Y =
1, 1 1, 1
| |
z
Y L Y

=
1,0 1,1
| | ?
z
Y L Y =
18_16fig_PChem.jpg
3-D Rotational motion & The Angular Momentum Vector
z
L m =
( 1) l l = + L
m indicates the orientation of
the angular momentum with
respect to z-axis
L
l determines the length
of the angular
momentum vector
Rotational motion is quantized not continuous. Only certain
states of motion are allowed that are determined by quantum
numbers l and m.
Three-Dimensional Rigid Rotor States
E
l
zm
L
l
E
,..,
l
m m
Y
3
3,2,1,0, 1, 2, 3
Y

2
2,1,0, 1, 2
Y

1
1,0, 1
Y

2
I
| |
|
\ .
6.0
3.0
1.0
0.5
0
3
2
1
0
Only 2 quantum numbers are require to determine the state of the system.
2
( 1)
2
l
E l l
I
= + ( 1)
l
L l l = +
z
L m =
12
6
2
L
m
0
1
0
-1
0
0
Y
1
0
-1
-2
2
1
0
-1
-2
2
-3
3
0
2
0
2
3
2
0
2
2
19_01tbl_PChem.jpg
Rotational Spectroscopy
19_13fig_PChem.jpg
2
2
( 1)
2
J
o
E J J
r
= +
1 J J
E E E
+
A =
| |
2
1 E J
I
A = +
J : Rotational quantum number
| |
2
2
( 1)( 2) ( 1)
2
o
J J J J
r
= + + +
2
( 1)
2
J
E J J
I
= +
hc
E h hc v v
A = = =
2
( 1)
4
h J
Ic
v
t
+
=
2 ( 1) B J v = +
2 2
8
o
h
B
r c t
=
Wavenumber (cm
-1
)
Rotational Constant
( )
1 J J
v c c v v v
+
A = A =
| |
2 ( 1 1) 2 ( 1) 2 c B J B J cB = + + + =
Frequency (v)
Av v
Line spacing
8 1 12
2 2 (2.99 10 / ) (1890 ) 1.13 10 v cB m s m Hz
A = = =
Predict the linespacing for the
16
O
1
H radical.
m
O
= 15.994 amu = 2.656 x 10
-26
kg
m
H
= 1.008 amu = 1.673 x 10
-26
kg
r = 0.97 A = 9.7 x 10
-11
m
1 amu = 1 g/mol = (0.001 kg/mol)/6.022 x 10
-23
mol
-1

= 1.661 x 10
-23
kg
27
26 27
1 1 1
1.774 10
2.656 10 1.673 10
kg
kg kg

= + =

2 2
8
o
h
B
r c t
=
( )( )
34 2
1
2
2 27 11 8
6.626 10 /
1890
8 1.774 10 9.7 10 (2.99 10 / )
kgm s
m
kg m m s t
= =

1 1 1
2 2 (1890 ) 3780 37.8 v B m m cm

A = = = =
The line spacing for
1
H
35
Cl is 21.19 cm
-1
,
determine its bond length .
m
Cl
= 34.698 amu = 5.807 x 10
-26
kg
m
H
= 1.008 amu = 1.673 x 10
-26
kg
27
26 27
1 1 1
1.626 10
5.807 10 1.673 10
kg
kg kg

= + =

2 2 2
8 8
o
o
h h
B r
r c B c t t
= =
( )
34 2
10
1 2 27 8
6.626 10 /
1.257 10 1.257
(1059.5 )8 1.626 10 (2.99 10 / )
kgm s
m A
m kg m s t

= = =

1
1
(21.19 )(100 / )
1059.5
2 2
v cm cm m
B m
A
= = =
x
y
z
d d
L i y z
dz dy
d d
L i z x
dx dz
d d
L i x y
dy dx
(
=
(

(
=
(

(
=
(

z
L m =
( 1) l l = + L
L
2 2 2 2

L
x y z
L L L = + +
?
?
,
( , )
l m
Y u |
z
L m =
2
( 1) L l l = +

x y z
i L L L = V = + + L r i j k
The Transverse Components of Angular Momentum
Y
lm
are eigenfunctions of L
2
and L
z
but not of L
x
and L
y
Therefore L
x
and L
y
do not commute with either L
2
or L
z
!!!
Commutation of Angular Momentum Components

,
x y x y y x
L L L L L L
(
=

d d d d d d d d d d d d
y z z x y z y x z z z x
dz dy dx dz dz dx dz dz dy dx dy dz
(
(
= +
(
(

2
2
2
d d d d d
y yz yx z zx
dx dzdx dz dydx dydz
= + +
2
d d d d d d d d
y z z x z x y z
dz dy dx dz dx dz dz dy

( (
( (
=
`
( (
( (

)
dz d d d d d d d d d
y z yx zz zx
dz dx dz dx dz dz dy dx dy dz
(
= + +
(

product rule
d d d d d d d d d d d d
z x y z z y z z x y x z
dx dz dz dy dx dz dx dy dz dz dz dy
(
(
= + +
(
(

2
2
2
d d d d d
zy z xy x xz
dxdz dxdy dz dy dzdy
= + +
d d d d d d dz d d d
zy zz xy x z
dx dz dx dy dz dz dz dy dz dy
(
= + + +
(

product rule
2
2
2
2
2
2
2

,
x y
d d d d d
y yz yx z zx
dx dzdx dz dydx dydz
L L
d d d d d
zy z xy x xz
dxdz dxdy dz dy dzdy

+ +

(
=
`

+ +

)
z
d d
i ih x y i L
dy dx
| |
(
= =
|
(

\ .

,
y x y x x y z
L L L L L L i L
(
= =

2
d d d d
y x i ih y x
dx dy dx dy
| |
(
= =
` |
(
)
\ .
2

x
d d d d d d d d
z x y z y z z x i L
dx dz dz dy dz dy dx dz

( (
( (
= =
`
( (
( (

)

,
x z x z z x
L L L L L L
(
=

2

y
d d d d d d d d
y z x y x y y z i L
dz dy dy dx dy dx dz dy

( ( ( (
= =
`
( ( ( (

)

,
z x z x x z y
L L L L L L i L
(
= =

,
y z y z z y
L L L L L L
(
=

,
z y z y y z x
L L L L L L i L
(
= =

Cyclic Commutation of Angular Momentum

,
z x y
L L i L
(
=

,
y z x
L L i L
(
=

,
x y z
L L i L
(
=

,
z y x
L L i L
(
=

,
x z y
L L i L
(
=

,
y x z
L L i L
(
=

,
x y z
L L i L
(
=

,
y x z
L L i L
(
=

x
L
y
L
z
L
i +

x
L
y
L
z
L
i
Commutation with Total Angular Momentum
2 2 2 2

, , , ,
z x z y z z z
L L L L L L L L
( ( ( (
= + +

2 2 2

,
x z x z z x
L L L L L L
(
=

, , ,
x z x z z x x z x z z x z x x z x z
L L L L L L L L L L L L L L L L L L
( ( (
= = + =

( ) ( )

, ,
x x z z x x z x z x
L L L L L L L L L L
( (
= +

x x z z x x
L L L L L L =

, ,
x x z x z x x z x x z x
L L L L L L L L L L L L
( (
= + +

x y y x
i L L i L L = +
2 2 2

,
y z y z z y
L L L L L L
(
=

, ,
y y z y z y y z y y z y
L L L L L L L L L L L L
( (
= + +

( ) ( )

, ,
y y z z y y z y z y
L L L L L L L L L L
( (
= +

, , ,
y z y z z y y z x z z y z y z y x z
L L L L L L L L L L L L L L L L L L
( ( (
= = + =

y x x y
i L L i L L = +

y y z z y y
L L L L L L =
2 2 2 2

, , , ,
z x z y z z z
L L L L L L L L
( ( ( (
= + +

2 2 2

,
z z z z z z
L L L L L L
(
=

0
z z z z z z
L L L L L L = =

0 0
x y y x y x x y
i L L i L L i L L i L L = + + + + =
2

, 0
x
L L
(
=

2

, 0
y
L L
(
=

This means that only
any one component of
angular momentum
can be determined at
one time.
Ladder Operators

x y
L L iL
+
= +

x y
L L iL
=
2

y x
i L i L =

y x
i L L = +

, , ,
z z x z y
L L L L i L L
( ( (
=

x y
L iL L
(
= =

, , ,
z z x z y
L L L L i L L
+
( ( (
= +

x y
L iL L
+
(
= + =

y x
i L L =

( )
y x
i L i i L =
Ladder Operators
What do these ladder operators actually do???
, , ,

l m x l m y l m
L Y L Y iL Y
+
= +
? ?
Recall That:
,
z
L L L
+ +
(
=

z z
L L L L L
+ + +
=
, ,

l m z z l m
L Y L L L L Y
+ + +
(
=

, , , ,

z l m z l m z l m l m
L L Y L L Y L L Y m L Y
+ + + +
= =
, , ,

l m z l m l m
L Y L L Y m L Y
+ + +
=
, ,

( 1)
z l m l m
L L Y m L Y
+ +
= +
, 1 , 1 , , 1

( 1)
z l m l m l m l m
L Y m Y L Y Y
' ' ' + + + +
= +
Raising Operator
Lowering Operator
, , 1
l m l m
L Y Y
'

Similarly
Therefore is an eigenfunction of with eigen values l and m+1
Ladder Operators
2 2 2

, , , 0 0 0
x y
L L L L i L L i
+
( ( (
= + = + =

2 2 2

, , , 0
x y
L L L L i L L
( ( (
= =

2 2 2
, ,

0 ,
l m l m
L L Y L L L L Y
+ + +
( (
= =

2 2
, ,

l m l m
L L Y L L Y
+ +
=
2 2
, ,

( 1)
l m l m
L L Y l l L Y
+ +
= +
2 2
, ,

( 1)
l m l m
L L Y l l L Y
+ +
( (
= +

,
l m
L Y
+
2

&
z
L L
Which implies that
, , , 1
l m l m l m
L Y C Y

=
Ladder Operators
, , , 1
l m l m l m
L Y C Y
+
+ +
=
, , , 1
l m l m l m
L Y C Y

=
This is not an eigen relationship!!!!
, l m
C
+
is not an normalization constant!!!
These relationships indicates that a change in state, by Am=+/-1, is caused by L
+
and L
-

Can these operators be applied indefinitely??
Remember that there is a max and min value for m, as
it represents a component of L, and therefore must be
smaller than L. ie.
( 1) ( 1) ( 1) m l l l l m l l < + + < < +
2,0 2,1
L Y Y
+

Why is
l = L
2,1 2,2
L Y Y
+

2,2
0 L Y
+

Not allowed
?
,
?
n
l m
L Y
+
(
=

,
?
n
l m
L Y
(
=

2,0 2, 1
L Y Y

2, 1 2, 2
L Y Y

2, 2
0 L Y

More Useful Properties of Ladder Operators
2 2 2 2

x y z
L L L L = + +
2 2 2 2

x y z
L L L L + =
2 2 2 2
, ,

x y l m z l m
L L Y L L Y
( (
+ =

2 2
, ,

l m z l m
L Y L Y =
( )
2
,
( 1)
l m
l l m Y = +
This is an eigen equation of a physical observable that is always greater than zero,
as it represents the difference between the magnitude of L and the square of its
smaller z-component, which are both positive.
2
( 1) 0 ( 1) ( 1) l l m l l m l l + > + < < +
This means that m is constrained by l, and since m can be changed by 1
, 1, 2,...., 2, 1, . m l l l l l l = + +
max
,
0
l m
L Y
+
=
min
,
0
l m
L Y
=
max
,

0
l m
L L Y
+
=
min
,

0
l m
L L Y
+
=
Lets show that m
min
and m
max
are l and -l resp.

& L L L L
+ +
Have to be determined in terms of
2

&
z
L L
2 2

2 2
z
L L L L L L
+ +
(
+ =

2 2

x y x y x x y y x y
L L L iL L iL L iL L iL L L
+
( (
= + = + +

2 2

x y x y x x y y x y
L L L iL L iL L iL L iL L L
+
( (
= + = + +

2 2
1

2
x y
L L L L L L
+ +
(
+ = +


, , ,
x y
L L L L i L L
+ + +
( ( (
=

, , , ( ) ,
x x y x x y y y
L L i L L i L L i i L L
( ( ( (
= + +

0 ( ) ( ) 0 2
z z z
i i L i i L L = + + =
Also note that:
2 2

, 2 2
z
L L L L L L L L
+ + +
(
+ =

2 2

z z
L L L L L
+
= +
2 2

z z
L L L L L
+
=
2 2

2 2
z
L L L L L L
+ +
+ =
2 2

2 2 2 2
z z
L L L L L
+
= +
Similarly
Ladder Operators
2 2
,max ,max

0
l z z l
L L Y L L L Y
+
(
= =

max max max
2 2
, , ,

l m z l m z l m
L Y L Y L Y =
( )
max max max
2 2 2
, max , max ,
1
l m l m l m
l l Y m Y m Y = +
( ) ( )
2
max max ,
1 ( 1)
l m
l l m m Y = + +
( )
max max
1 ( 1) 0 l l m m + + =
max
m l =
Ladder Operators
min min
2 2
, ,

0
l m z z l m
L L Y L L L Y
+
(
= = +

min min min
2 2
, , ,

l m z l m z l m
L Y L Y L Y = +
( )
min min min
2 2 2
, min , min ,
1
l m l m l m
l l Y m Y m Y = + +
( ) ( )
min
2
min min ,
1 ( 1)
l m
l l m m Y = +
( )
min min
1 ( 1) 0 l l m m + =
( )
2
min min min
1 0 1, & m m l l m l l + = =
Since the minimum value cannot be larger than the maximum value, therefore .
min
m l =

Rotational Motion 2009 7

Enviado por

Dados do documento

Direitos autorais

Formatos disponíveis

Compartilhar este documento

Compartilhar ou incorporar documento

Opções de compartilhamento

Você considera este documento útil?

Este conteúdo é inapropriado?

Direitos autorais:

Formatos disponíveis

Rotational Motion 2009 7

Enviado por

Direitos autorais:

Formatos disponíveis

18_12afig_PChem.

Linear momentum of a rotating Body

The spherical Harmonics

Você também pode gostar