Lecture 9: Variational method:

molecules (10/18/2005)
Today, we will look how the energy spectrum of molecules may be calculated
in quantum mechanics. Our basic example will be the hydrogen molecule ion
(or H2+ molecule). We will see how the Born-Oppenheimer approximation
and the variational method helps to calculate such systems. Finally, we will
see that the molecules possess two additional layers of finer structure of their
spectrum: vibrational modes and even tinier rotational modes.
Additional reading if you wish: Griffiths 7.3, Gasiorowicz 20

Hydrogen ion molecule

What is the simplest molecular system? We need more than one proton; the
smallest integer greater than one is two. And we need at least one electron;
the smallest number that is at least one is one. The system with two protons
and one electron is called H2+ the hydrogen molecule ion.

Born-Oppenheimer approximation
The exact solution would involve a wavefunction of 3 vectors in three dimensions one electrons vector and two protons vectors. The center-of-mass
vector could be decoupled, but we would still deal with nontrivial wavefunctions that depend on the remaining two relative vectors.
Fortunately, protons are much heavier than the electron and their motion is much slower which allows us to treat their positions and momenta
classically in the first approximation. This approach is called the BornOppenheimer approximation: we first assume that the positions of protons
are fixed well-defined numbers and calculate the motion of the electron(s)
in the external potential produced by the protons. In doing so, we simply
neglect the kinetic energy of the protons because it is tiny compared to the
electrons kinetic energy (recall it is p2 /2m and p is comparable while m
is much greater for protons). Once we obtain the energy spectrum of the
electrons, which will be a set of functions that depend on the positions of
the protons, we may treat the energy eigenvalues as potential energy for
the positions of protons, and solve the Schrodinger equation for the protons
positions.
1

Gerade and ungerade

Draw the following graph of energy E as functions of the separation R
between the protons: the repulsive (positive) Coulomb energy between
the protons that goes like 1/R; then the negative energy coming from the
electron-induced electronic energy that is increasing from E = 413.6 eV
at R = 0 towards E = 0 at R ; and then their sum, the nuclear potential that is minimized at a finite value of R, the equilibrium separation.

Let us adopt the following notation:

~r1 , ~r2 are the relative positions of the electron with respect to the two
protons
r1 , r2 are the lengths of these two vectors, i.e. the distances of the
electron from the proton
R is the distance between the protons electron
The Hamiltonian for the molecule ion is
e2
h
2 2

H=
2m
40

1
1
1
+
r1 r2 R

and it acts on the wavefunction (~r) that only depends on the position of the
electron. We first treat R, the distance between the protons, as a classical
acting on the wavefunctions (~r)
constant. Lets also define an operator
that rotates (or reflects) the space by in such a way that the protons are
interchanged. This operator commutes with the Hamiltonian:
H] = 0
[,
The energy eigenstates are therefore eigenstates of , too. Note that if the
wavefunction (~r) only depends on the distances r1 , r2 (and not the third
is
coordinate, an angle ), then the action of

(r
1 , r2 ) = (r2 , r1 ).
A simple choice of trial functions for the electron is
1
g (~r) = [0 (r1 ) + 0 (r2 )]
2
1
u (~r) = [0 (r1 ) 0 (r2 )]
2

gerade
ungerade

where the word gerade means straight or even in German (much like
ungerade is odd) and where
1 r/a
e
0 (r) =
a3
is the Hydrogen atom ground state wavefunction. You see that we have used
linear combinations of atomic orbitals, which is why the method is called
LCAO. Draw schematically the functions u,g and the probability distributions |u,g |2 on the axis connecting the protons! They are not continuous
near the nuclei and u vanishes in the middle.

Computing the expectation values

We need to calculate and minimize
Eg,u (R) =

hg,u |H|g,u i
.
hg,u |g,u i

Lets start with the denominator because it is simpler.

1
h0 (r1 ) 0 (r2 )|0 (r1 ) 0 (r2 )i
hg,u |g,u i =
2
= h0 (r1 )|0 (r1 )i h0 (r1 )|0 (r2 )ireal
= 1I

(1)

We normalized the atomic wavefunction to one. Surprisingly, the overlap

integral I of the two-center kind can again be solved in closed form.
You may see Griffiths book for another method. Our method will be slightly
different and it will start with the following basic generating integral:
er1 er2
4 eR eR
I1 =
dr
=
r1 r2
R 2 2
2 R

e
for =

We may obtain the results for new integrals by differentiating the integral
above:
Z
r1 r2
e
dI1
3 e
=
dr
I2
d
r1
"
#
R
4 Re
2(eR eR )
=

R 2 2
(2 2 )2

(1 + R)eR for =
2
Z
dI2
=
d3 rer1 er2
I3
d
"
#
4(eR eR )
8
R
R
R(e
+ e
)+
=
R(2 2 )2
2 2


1

1 + R + 2 R2 eR for =

3
Z

The overlap integral is proportional to I3 :

1
d3 r er1 /a er2 /a
I(R) =
a3
!
1
R 1 R2 R/a
=
I3 (==a1 ) = 1 + +
e
a3
a
3 a2
Z

Note that the result is almost monotonically decreasing from I(0) = 1 to

I() = 0. We may repeat the procedure for the numerator which contains
an additional insertion of H.
1
1
h|H|i =
h0 (r1 )|H|0(r1 )i + h0 (r2 )|H|0 (r2 )i
2
2
1
1
h0 (r1 )|H|0(r2 )i h0 (r2 )|H|0 (r1 )i

2
2
= h0 (r1 )|H|0 (r1 )i h0 (r1 )|H|0 (r2 )i
H11 + H12
Lets start with H11 , the diagonal term of the full Hamiltonians matrix
element:
H11 =
=
=
=

h
2 2
e2
1
1
1
h0 (r1 )|

+
|0 (r1 )i
2m
40 r1 r2 R
 
e2
1
e2

h0 (r1 )|
E1 +
|0 (r1 )i
40 R 40
r2
"
#
I2 ( = 0, = 2/a)
e2
1

E1 +
40 R
a3




1
1
1 2R/a
e2
1
+
+
E1 +
e
40 R R
a R
"

#

Recall that because the Hydrogen ground state energy is

e2 1
E1 =
40 2a

H11 = E1

a 2R/a
12 1+
e
R


Surprisingly, the H12 term wont be more difficult:

H12 =
=
=
=
=

h
2 2
e2
1
1
1
|0 (r2 )i
h0 (r1 )|

+
2m
40 r1 r2 R
!
e2
e2
h0 (r1 )| E1 +

|0 (r2 )i
40 R 40 r1
!
e2
e2
I2 (==1/a)
E1 +
I
40 R
40


e2
2R R/a
1
E1 I +

e
40 R 3a2




2R R/a
a
e

E1 I 2
R
3a
"

#

Summarizing the results

The final result for the average energy is thus

)eR/a
h|H|i
2 (R + a)e2R/a (a 2R
3a
= 1
2
R
R/a
h|i
R
1 (1 + Ra + 3a
2 )e
The energy of the ungerade solution (with the minus sign) will always be
above E1 and it does not bind. This is why the gerade solution (with the
plus sign) is the only interesting one. If we minimize its energy with respect
to R, we obtain a minimum at
R = 1.32
A

Eg (R) = (13.6 + 1.76) eV

where 1.76 eV (or perhaps 1.77 eV) is the binding energy compared to a
Hydrogen atom plus a proton. Because we used the variational method, the
exact Eg (R) is actually lower for every R. Also, its minimum at
R = 1.06
A

Eg (R) = (13.6 + 2.8) eV

is thus lower than our calculated minimum. Refine the previous graph.
Questions
Is our trial function exact in the limit R ? Is it exact for R 0? How
could you improve the variational calculation?

Molecular vibrations
So far we have treated the distance R between the protons as a classical
number; the corresponding velocity may more or less be set to zero because
it is suppressed by m/M relatively to the electronic velocities. Let us now
try to take these effects into account. The calculated energy eigenvalue of
the electron Eg (R) may be interpreted as the nuclear potential between
the protons.
If you know what is the path integral approach, you may also say that we have
integrated out the fast, electronic degrees of freedom, to get effective dynamics for
the slow motion of the protons (i.e. for very low-energy physics).

h
2 2

+ Eg (R) = E(R)
2m R
!

We have essentially set the motion of the electron to its R-dependent ground
state and we now only consider the splitting of this ground state induced by

the motion of the protons. Expand the potential energy Eg (R) around its
minimum at R = R0 :
2 Eg (R)
1
Eg (R) Eg (R0 ) + (R R0 )2
2
R2

.
R=R0

The linear term disappeared because we are near the minimum and the
higher-order terms are unimportant if we only study the lowest possible energy states. You can see that the Hamiltonian for R is nothing else than
the harmonic oscillator. Its spectrum and the vibration spectrum of the
molecule ion is
Evib

1
h

= n +
2


with

v
u
u
t

1
M

2 Eg (R)
R2

.
R=R0

Here, M is really the reduced mass for the two-proton problem, M = mp /2.
To make an order-of-magnitude estimate of the vibrational frequencies, realize that E(R) is of order e2 /40 R and its second derivative is therefore
2 Eg (R)
R2
For R0 2a, we obtain
h

v
u
u
t

R=R0

h
2 e2

40 4ma3

2e2
.
40 R03

me
|E1 |.
M

Because M is greater by three orders of magnitude than me , the vibrational

spectrum is finer by 1 or 2 orders of magnitude compared to the atomic
spectrum. If you substitute the numbers for the H2+ molecule, you obtain
h
0.1 eV.

Molecular rotations
The molecule does not rotate around its axis by rotating, you dont get
new states. But you can rotate around the other two independent axes.
Such rotations will contribute to the centrifugal potential:
L2x + L2y
L2 L2z
l(l + 1)
h2
=
=
.
MR2
MR2
MR2
For R0 2a and l 1, this is of order
Erot =

Erot

h
2
h
2 me
me
el. me

E
1
kin
Ma2
me a2 M
M
M

which is three or four orders of magnitude below the electronic energies and
the corresponding transitions emit photons in the microwave region. To summarize: molecules have electronic levels that are split into finer vibrational
levels, with each vibrational level split into rotational levels.
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