Chemistry 431

Lecture 6
Rotational motion

NC State University

Classical Rotation
In a circular trajectory Jz = pr and E = Jz2/2I.
I is the moment of inertia.
Diatomic I = r2

Mass in a circle I = mr2.

r

m1

m2
m 1m 2

=
Reduced mass
m1 + m2

Rotation in two dimensions

The angular momentum is Jz = pr.
Jz
r
m

Using the deBroglie relation p = h/ we also

have a condition for quantization of angular
motion Jz = hr/.

The 2-D rotational hamiltonian

The wavelength must be a whole number
fraction of the circumference for the ends to
match after each circuit.
The condition 2r/m = combined with the
deBroglie relation leads to a quantized
expression,Jz = mh.
2 2
The hamiltonian is: h 2 = E
2I

The 2-D rotational hamiltonian

Solutions of the 2-D rotational hamiltonian are
sine and cosine functions just like the particle in
a box.
Here the boundary condition is imposed by the
circle and the fact that the wavefunction must not
interfere with itself.
The 2-D model is similar to condition in the Bohr
model of the atom.

The 2-D rotational hamiltonian

The wavelength must be a whole number
fraction of the circumference for the ends to
match after each circuit.
The condition 2r/m = combined with the
deBroglie relation leads to a quantized
expression,Jz = mh.
2 2
h
The hamiltonian is:

2I

= E

Quantization of rotational motion:

solution of the equation
The corresponding wavefunctions are:

1
m=
2

1/2

with the constraint that:

2IE
m=
h

im

1/2

Since the energy is constrained to values Jz2/2I we find that

m = 0, 1, 2, ...

The wavefunctions of a rigid rotor are

called spherical harmonics
The solutions to the and equation (angular part)
are the spherical harmonics Y(, )= ()()
Separation of variables using the functions ()
and () allows solution of the rotational wave
equation.
2
h

Y
1 sin Y
1

2I sin 2 2 sin
2

= EY

We can obtain a and equation from the above

equation.

Spherical Polar Coordinates

z

r
r cos()
x

r sin() sin()

r sin() cos()

The volume element in spherical

polar coordinates
To solve the Schrodinger equation we need to
integrate of all space. This is the same thing
as performing a volume integral. The volume
element is:

dV = r 2dr sind d
This integrates to 4, which is the
normalization constant. 4 stearadians also
gives the solid angle of a sphere.

Separation of variables
The spherical harmonics arise from the product
of after substituting Y =

2 + sin sin = sin 2E

2
For sake of simplicity, we have factored the term
2

2I

into the energy. At the end of the calculation we

Will multiply by this term to obtain the energy.

Separation of variables
The operators in variables and operate on functio
and , respectively, so we can write
2
2 + sin sin = sin E

When we divide by Y = , we obtain

2

1 + 1 sin sin sin 2E = 0

2

Now, these equations can be separated.

Separation of variables
We use a separation constant equal to m2 to write
two equations. The and equations are
sin sin

2
1
2

sin E = m 2
2

= m2

We have already seen the solution to the equation

from the example of rotation in two dimensions.

The solution of equation gives

Legendre polynomials
Substitute x = cos and the equation becomes:
2

P
m
P
1x
2x
+ E
P=0
2
2
x
1x
x
2

The solution requires that =-(h2/2I)J(J+1) with J=0,1,2

Where J is the rotational quantum number.
The azimuthal quantum number m is also called Jz.
The magnitude of |Jz|<J. The solutions are Legendre
polynomials
P0(x)=1
P2(x)=1/2 (3x2 - 1)
P1(x)=x
P3(x)=1/2 (5x3 - 3x)

The spherical harmonics as solutions to

the rotational hamiltonian
The spherical harmonics are the product of the
solutions to the and equations. With norm-alization these solutions are

Y (,) = NJMP (cos )e

M
J

|M|
J

iM

The M quantum number corresponds to Jz the

z component of angular momentum. The norm-alization constant is
NJM

(J |M|)!
2J
+
1
=
2 (J + |M|)!

1/2

The form of the spherical

harmonics
Including normalization the spherical harmonics are

Y00 = 1
4
0
3 cos
Y1 = 4
1
Y1

Y2 =
1
2

Y =

3 sine i 2
Y2 =
8

5 3cos 2 1
16
15 sincose i
8
15 sin 2e 2i
32

The form commonly used to represent p and d

orbitals are linear combinations of these functions

Euler relation
Linear combinations are formed using the Euler relatio

e i = cos isin
i
i
sin = e e
2i
i
i
+
e
e
cos =
2
Projection along the z-axis is usually taken using
z = rcos. Projection in the x,y plane is taken using
x = rsincos and y = rsinsin

The 3-D rotational hamiltonian

There are two quantum numbers
J is the total angular momentum quantum number
M is the z-component of the angular momentum
The spherical harmonics called YJM are functions whose
probability |YJM|2 has the well known shape of the s, p
and d orbitals etc.
J = 0 is s , M = 0
J = 1 is p , M = -1, 0 , 1
J = 2 is d , M = -2 , -1, 0 , 1, 2

Space quantization in 3D
Solutions of the rotational
Schrdinger equation have

z
M = +2
M = +1
M=0
M = -1
M = -2
J=2

energies E = h2 J(J +1)/2I

Specification of the azimuthal
quantum number mz implies
that the angular momentum
about the z-axis is Jz = hmz.
This implies a fixed orientation
between the total angular
momentum and the z
component.
The x and y components
cannot be known due to the
Uncertainty principle.

Spherical harmonic for

P0(cos)
Plot in polar coordinates
represents |Y00|2 where
Y00=(1/4)1/2 .
Solution corresponds to
rotational quantum numbers
J = 0,
M or Jz = 0.
Polynomial is valid for n1
quantum numbers of
hydrogen wavefunctions

Spherical harmonic for

P1(cos)
Plot in polar coordinates
represents |Y11|2 where
Y11=(1/2)(3/2)1/2 sinei.
Solution corresponds to
rotational quantum
numbers J = 1, Jz = 1.
Polynomial is valid for
n2 quantum numbers of
hydrogen wavefunctions

Spherical harmonic for

P1(cos)
Plot in polar coordinates
represents |Y10|2 where
Y10=(1/2)(3/)1/2 cos
with normalization.
Solution corresponds to
rotational quantum
numbers J = 1, Jz = 0.
Polynomial is valid for
n2 quantum numbers of
hydrogen wavefunctions.

Spherical harmonic for

P2(cos)
Plot in polar coordinates
of |Y22|2 where
Y22=1/4(15/2)1/2cos2e2i
Solution corresponds to
rotational quantum
numbers J = 2, Jz = 2.
Polynomial is valid for
n3 quantum numbers of
hydrogen wavefunctions

Spherical harmonic for

P2(cos)
Plot in polar coordinates
of |Y21|2 where
Y21=(15/8)1/2sincosei
Solution corresponds to
rotational quantum
numbers J = 2, Jz = 1.
Polynomial is valid for
n3 quantum numbers of
hydrogen wavefunctions

Spherical harmonic for

P2(cos)
Plot in polar coordinates
of |Y20|2 where
Y20=1/4(5/)1/2(3cos2-1)
Solution corresponds to
rotational quantum
numbers J = 1, Jz = 0.
Polynomial is valid for
n3 quantum numbers of
hydrogen wavefunctions

Rotational Wavefunctions

J=0

J=1

J=2

These are the spherical harmonics YJM, which

are solutions of the angular Schrodinger equation.

The degeneracy of the

solutions
The solutions form a set of 2J + 1 functions at each
energy (the energies are E = h2 J(J +1)/2I.
A set of levels that are equal in energy is called a
degenerate set.

J=3
J=2
J=1
J=0

Rotational Transitions
Electromagnetic radiation can interact with a molecule to
change the rotational state.
Typical rotational transitions occur in the microwave
region of the electromagnetic spectrum.
There is a selection rule that states that the quantum
number can change only by + or - 1 for an allowed
rotational transition (J = 1).
J=2
J=1
J=0

Orthogonality of
wavefunctions
The rotational wavefunctions can be represented as the
product of sines and cosines.
Ignoring normalization we have:
s 1
p cos sincos sinsin
d 1/2(3cos2 - 1), cos2cos2 , cos2sin2 ,
cossincos , cossinsin
The differential angular element is sindd/4 over
the limits = 0 to and = 0 to 2.
The angular wavefunctions are orthogonal.

Orthogonality of
wavefunctions
For the theta integrals we can use the substitution
x = cos and dx = sind
For example, for s and p-type rotational wave functions we
have

<s|p>

cos sin d =
0

2
x
x dx =
2

= 1 1 =0
2 2

Question
Which of the following statements is true:
A. The number of z-projection of the quantum numbers is
2J+1.
B. The spacing between rotational energy levels increases
as 2(J+1).
C. Rotational energy levels have a degeneracy of 2J+1.
D. All of the above.

Question
Which of the following statements is true:
A. The number of z-projection of the quantum numbers is
2J+1.
B. The spacing between rotational energy levels increases
as 2(J+1).
C. Rotational energy levels have a degeneracy of 2J+1.
D. All of the above.
E ~ (J +2)(J + 1) J(J + 1) = 2(J + 1)

Question
The fact that rotational wave functions are orthogonal means
that
A. They have no overlap
B. They are normalized
C. They are linear functions
D. None of the above

Question
The fact that rotational wave functions are orthogonal means
that
A. They have no overlap
B. They are normalized
C. They are linear functions
D. None of the above

The moment of inertia

The kinetic energy of a rotating body is 1/2I2.
The moment of inertia is given by:

I=

mr

i=1

2
i i

The rigid rotor approximation assumes that

molecules do not distort under rotation. The types
or rotor are (with moments Ia , Ib , Ic)
- Spherical: Three equal moments (CH4, SF6)
(Note: No dipole moment)
- Symmetric: Two equal moments (NH3, CH3CN)
- Linear: One moment (CO2, HCl, HCN)
(Note: Dipole moment depends on asymmetry)
- Asymmetric: Three unequal moments (H2O)

The rotational partition function

The degeneracy of rotational levels is J(J+1).
The energies are given by = hcBJ(J+1) where
J is the rotational quantum number and B is the
rotational constant.

qr =

J=0

(2J + 1)e

hcBJ(J + 1)

A large number of rotational levels populated since

the rotational constant is of the order of 10 cm -1 for
many molecules and kT > 10 cm-1 for temperatures
higher than about 15 K.

The high temperature form of the

rotational partition function
The partition function can be expressed as an
integral at high temperature.

qr =

(2J + 1)e hcBJ(J + 1)dJ

It turns out that the integral can be solved

analytically by making the substitution u = J(J+1).

u = J(J + 1), du = (2J + 1)dJ

The rotational partition function

is an exponential integral
Making the substitution u = J(J+1) the integral
reduces to an easily soluble exponential integral.

qr =

e
0

hcBu

1
du =
hcB

The rotational constant B is:

B=

h where I is the moment of inertia

4cI