5.

61 Fall, 2013

Lecture #17

Page 1

Lecture #17: Rigid Rotor II

Last time:
1.

Analogy between linear and angular momenta

Momentum =
p

L (or J )

(mass factor)

I
=
r02
(the mass factor is more
complicated for polyatomic
molecules)

(vector velocity factor)

v

(z means angular velocity

about the z-axis)

2.

Transformation to molecular center-of-mass coordinate system permits replacement of

m1, m2, by .

3.

Rigid rotor is either free rotation of

m1

r1

r2

m2

center
of mass
a dumbbell or free motion of a mass particle confined to the surface of a sphere.
4.

Transform kinetic energy from Cartesian to spherical polar coordinates. Since there is no

r-motion, the
derivatives are all zero and we have a , differential equation. The ,
r
equations may be separated following a procedure analogous to what we used to separate
x, y, and z for the 3-D box.
The differential equation is simple, giving normalized eigenstates
M ( ) = ( 2 )1/2 eiM
M is an integer L M L

The differential equation (Legendre equation) is not simple.

Eigenfunctions are:

Spherical Harmonics, YLM ( , )

YLM ( , ) and PLM ( cos ) are differently normalized functions.

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Lecture #17

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2L + 1 ( L M )!
PLM ( cos ) eiM
Y ( , ) =

4 ( L + M )!
1/2

M
L

Notice that the form of the dependence depends on the value of the quantum number,
M. A consequence of the separation of variables procedure.
Today:
1.

Rotational Spectra. A way to measure molecular geometry by a surprisingly indirect

path.
Why not just put a ruler on it?

2.

3.

Visualization of the YLM ( , ) functions.

* polar plot
* real vs. complex representations
A wavefunction and differential operator-free approach via Li , L j = in ijk L k
k

commutation rules.

This is how we define and work out the properties of multiple angular momenta

(selection rules and matrix elements). A very powerful algebra.

L2 L,M L = n 2 L ( L + 1) L,M L
= nM
L
z

L,M L

L,M L

L L x iL y
1/2
L L,M L = n L ( L + 1) M L ( M L 1) L,M L 1

We are going to derive all of this from commutation rules.

But first, spectra

H rot
H

free
rotation

n
= TH rot + 0 =

cm -1
units

n
L2
hc B 2
L

2 r02
n2

hcB 2
H rot
H
n L ( L + 1) L,M L
L,M L =
n2
E / hc = BL ( L + 1)
A rotational spectrum requires that a molecule has a permanent electric dipole moment, . This
dipole moment is the handle torqued by the electric field of the photon.

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Lecture #17

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For example:

+
H Cl

Selection rule is L = 1, ML = 0, 1

(ad hoc, Sorry!)

EL/hc = BL(L + 1)

Transition
E/hc

2B

(2 0)B

10
2B

4B

(6 2)B
21
2B

32

6B

(L + 1) L

2(L + 1)B

(12 6)B

[(L + 1)(L + 2) L(L + 1)]

Spectrum:

2B

4B

6B

8B

E/hc

Assignment seems to be trivial but is not, because typical microwave oscillators cover only
a , + 0.3 30% band.
Typically, for light diatomic molecules, only one rotational line per molecule appears in the
spectrum. What can we do to put rotational quantum number assignments onto the
spectral lines?
Isotope shift (light and heavy isotopes of atom #1)

H35Cl

L =

m1L m2
L = L
m1 + m2

m1H m2
H = H
m1 + m2

35
= 0.9722
36

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5.61 Fall, 2013

H37Cl

Lecture #17

H =

37
= 0.9737
38

Page 4

L
= 0.9985
H

Not too small! Very high precision in spectrum, typically better than 1 part in 105!

L
, know masses, natural abundance. Assign L, L + 1 transition to determine
H
B. Get r0 from B.
BH = BL

What is wrong with this argument? (Depends on seeing a pattern when the observed
spectrum contains only one transition.) What additional information can we bring to this
problem? Isotope shifts will not be sufficient. Why? What works?
Visualization of YLM ( , ) .
You already know polar plots of s, p, d, f atomic orbitals from 5.111, 5.112. Same thing.
But

what are they really and how do they ENCODE L, ML and the direction that L is
pointing?
Polar plot: (r, ,) is a point in 3D spherical polar coordinates.
The trick is that we plot, for each ,

r=

1
L,M L ( , ) L M L ( , )
2
Top sign makes the thing we plot a real number
even though L,M L has a complex eiM L phase
factor. What does the bottom sign give?

We plot a point located at (r,,) that tells the magnitude of in the , direction.
The things we plot are not eigenfunctions of L z (why not?), but they are eigenfunctions of
H and L2 .
H

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5.61 Fall, 2013

Nodes remain!

Lecture #17

L = 0 zero
1 one

Page 5

angular nodes

2 two

If angular momentum is about z-axis, ML = L and maximum amplitude of is mostly in the

plane to z-axis.

(,) is the probability amplitude of what? L or the internuclear axis?

L
Be careful! Primary
amplitude
of

is
NOT
along
the
angular
momentum
vector,
. It is in the

*
plane to L . We could have plotted L,M L L,M L , but this loses the phases, which are
important for understanding Quantum Mechanical interference effects. It does preserve
nodal surfaces, and you know that the phase reverses on opposite sides of a nodal surface.
Commutation Rule Algebra the general definition of angular momenta.

L=r p
There is no spatial coordinate associated with electron and nuclear (NMR!) spins. But we want
to think of them as angular momenta.

J = L + S
This coupling of different types of angular momenta is

observable in many kinds of spectra
F = J + I
So we adopt a formal, general approach.

Any angular momentum must obey this general commutation rule. Use L for illustration.

Li , L j = in ijk Lk

ijk Levi-Civita symbol (i, j, k are Cartesian axis labels)

ijk = +1 if

x, y, z are in standard cyclic order

xyz, yzx, zxy

ijk = 1 if
ijk = 0 if

anti-cyclic order, e.g. zyx, xzy, yxz

two indices are identical, e.g. xxy

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Lecture #17

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We want to derive all of the properties of angular momentum operators, operating on angular
momentum eigenstates without ever looking at the differential operator form of the
operators or the functional form of the eigenfunctions. We always start with the
fundamental equation

Li , L j = in ijk L k .
k

First we need to derive some commutation rule results using the general commutation rule above.
=0
n
L2 , L z = L2x , L z + L2y , L z + 2
Lz , Lz
= L x L x , L z + L x , L z L x + L y L y , L z + L y , L z L y
= L x inL y + inL y L x + L y ( inL ) + ( inL ) L y

) (

= 0.
[This nicely illustrates the power of ijk algebra!]
Generalize

L2 , L = 0

(for all 3 components of L ).

But the one we really care about is

L2 , L z = 0 .
Because this means we can have simultaneous eigenstates of L 2 and L z.
We need to work out one other commutation rule result:
L L x iL y



Lz , L = Lz , Lx i Lz , Ly
= inL y i ( inL )

= n L x iL y = nL .

Also, by inspection

L2 , L = 0 .
H2,L
H z , and the effects of L
H without ever looking at a
We are going to derive the eigenvalues of L
wavefunction or a differential operator.
Suppose f is an eigenfunction of L 2 with eigenvalue and of L z with eigenvalue , then

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Lecture #17

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L2 f = f
L z f = f .

1.

Show that ( L f ) is eigenfunction of both L 2 and L z. L 2, L

commute, thus

L2 ( L f ) = L ( L2 f ) = ( L f )
L f is eigenfunction of L 2 with eigenvalue (same as that of f). Operation by
L does not affect the value of .

2.

Now, use L z , L = nL .
L z L L L z = nL
L z f
= n ( L f )
L z ( L f ) L
f

L z ( L f ) = L ( f ) n ( L f )
= ( n ) ( L f ) .

Thus, L f is eigenfunction of L z belonging to eigenvalue n.

We have a ladder of states increasing in by steps of n. The ladder must be finite because a

projection of L cannot be larger than L .

3.

Use fact that there must exist a maximum value of .

L + fmax = 0
L z f max = nffmax

(we really do not know yet that f is integer or

half-integer or anything)

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4.

Lecture #17

Page 8

We need to derive another important operator equation.

(
= ( L

)(
)
+ L ) iL L iL L

L L = L x iL y L x iL y
2
x

2
y

= L2 L2z i L y , L x
= L 2 L2z nL z
= L2 L2z i inL
z

rearranging

L2 = L2 z nL z + L L
5.

Use this boxed equation to find the value of for top rung of ladder:

L2 fmax = L L fmax + L2z fmax nL z fmax

use lower sign
= 0 + ( nf )2 fmax + n 2 ffmax
= n 2 ( f2 + f ) fmax .
Thus , an eigenvalue of L 2, is = n2f(f + 1).
6.

Similar argument (top signs) for of lowest rung of ladder.

L2 fmin = L + L fmin + L2z fmin nL z fmin

=0

Let L z fmin = n
f fmin
we do not know what this f is, no
assumption is being made here.

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L2 fmin = 0 + n 2 f 2 fmin n 2 ffmin

fmin = n 2 ( f 2 f ) fmin
so = n 2 f ( f 1).
7.

Putting it all together:

we saw previously = n2f(f + 1), now we also require = n 2 f ( f 1) , thus

f ( f + 1) = f ( f 1)
f2 + f = f 2 f
so we have 2 possibilities

f = f

OR
f = f+1
This second possibility cannot be correct
because we know that L lowers .
Thus we are left with the following results:
f = f

min =
max
= n 2 f ( f + 1)

= ( f,f 1, f ).

8.

We are not quite done. 2 possibilities.

f is integer or half-integer. Cannot get, in steps of 1, from +f to f if f is neither integer
nor half-integer.
This is not a defect! We can have half-integer angular momenta, like electron spin S =
or some nuclear spins I = 1/2, 3/2, 5/2 (as in H, Cl, 17O). Our formalism deals with both
integer and half-integer angular momenta!

9.

What about the effect of L on L,M L ? We are going to prove that

1/2
L L,M L = n [ L(L + 1) M L (M L 1)] L,M L 1 .

We are going to examine the LHS and RHS of this equation.

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Lecture #17

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Use
L2 = L2z nL z + L L ,

rearrange

L L L,M L = L2 L2z nL z L,M L

= ( n 2 L ( L + 1) n 2 M L2 n 2 M L ) L,M L

= n 2 L
( L + 1) M L ( M L 1) L,M L ,
multiply on left by *L,M L and integrate:
RHS = n 2 L
( L + 1) M L ( M L 1)
Now use property of complex conjugation:
*
= * L = X *
L

L,M L

LHS =

L,M L

X * Xd =

2
X d =

c L,M L 1 d = c

L L,M L c L,M L 1

thus

c = n L ( L + 1) M L ( M L 1)

1/2

and this gives us the last of our results. Note that the sign of

L L,M L = ( sign ) n L
( L + 1) M L ( M L + 1) L,M L 1 is undetermined. One must
make a phase choice and stick to it because we have no actual wavefunctions or
differential operators to check for internal phase consistency. This is a minor (but not
ignorable) cost of using this elegant operator algebra.
1/2

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5.61 Physical Chemistry

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