Chem 441 Quantum Chemistry Notes May2, 2003 rev

VI. Approximate Solutions

A. Variation Method and Huckel Molecular Orbital (HMO) Calculations

References: Liberles, Ch. 4, Atkins, Ch. 8, Pauling and Wilson
Streitweiser, "MO Theory for Organic Chemists"
Bauer, H; Roth, K. "The Numeric Solution of Eigenvalue Problems", J. Chem. Educ., 1980, 57, 422-424.
Consider the Schrodinger Equation: e ψ ψ =
∼ ∼
H (1)
Where ψ

is an approximate solution to a particular problem and is an accurate Hamiltonian operator for that problem.
A key difference in this approximate case is that the energy e is not constant (unless, of course, the approximate solution
happens to be exact!). Now, consider the following operations on (1):
H
Multiply both sides by * ψ

: * *e e * ψ ψ ψ ψ ψ ψ = =
∼ ∼ ∼ ∼ ∼
H

(2)

(note that e and
*
ψ

commute, but and H
*
ψ

cannot commute.)
Now note that
*
*
d
d
ψ ψ τ
ψ ψ τ

∼ ∼
∼ ∼
(3)
is the probability of finding a particle in the region dτ. (The integral in the denominator is over the entire region of space
where the particle described by ψ

could be found. It has the value 1 if ψ

is normalized.)
Thus it is reasonable to claim that
*

*
d
e
d
ψ ψ τ
ψ ψ τ

∼ ∼
∼ ∼
represents the probability of finding the particle with energy e. Using
this idea, we can claim that the average value of the energy is the sum of such terms over all points in space:

* *
*
* * *
e d
E
d
ψ ψ τ ψ ψ
ψ ψ
ψ ψ τ ψ ψ ψ ψ
< >
= = =
< >
∫ ∫
∫ ∫
∼ ∼ ∼ ∼
∼ ∼
∼ ∼ ∼ ∼ ∼ ∼
H
H
(4)
(The <...> symbols in * ψ ψ <
∼ ∼
> are simply a shorthand notation for integration over the entire space where the particle
described by ψ

might be found.)

An important theorem about <E>
o
is the
0 0,
Variation Theorem:
exact
E E < > ≥ (5)
Proof: let
n n
n
c ψ ψ =


where
n
ψ is an exact solution with eigenvalue E
n
.
Plugging this into (4) we have:
* *
2 *
*
m m n n m m n n
n n n n
n n n
m m n n
n
n n
c c c c
E
c
c c
ψ ψ ψ ψ
ψ ψ
ψ ψ
| | | | | ||
| | |
\ . \ . \ .\
= =
| || |
| |
\ .\ .
∑ ∑ ∑ ∑
∫ ∫


∑ ∑

H H
|
|
.
=


* 2 * 2
2
2 * 2 *
m m n n n n n n n n n
n n n
n
n n n n n n
n
n n
c c E E c E c
c
c c
ψ ψ ψ ψ
ψ ψ ψ ψ
| || |
| |
\ .\ .
= =
∑ ∑ ∑ ∑ ∫ ∫
n

∑ ∑
∫ ∫
(6)
Page 1
which can be rearranged to:
2
o n n
E c E =
∑ ∑
2
n
c where we have assumed that the approximate energy will be an
approximation to the lowest E level. Consider now:
2 2
, ,
0
o o exact n n o exact n
E E c E E c − = −


∑ ∑

Hence, <E
o
>
>
_ E
o,exact
QED.

Problem 1. Prove that all the steps in (6) are correct.
Problem 2: The substitution:
n n
n
c ψ ψ =


is reasonable if it is a general way of
describing any possible approximate wave function. We can prove that this is the case by showing how to
obtain a general formula for c
k
. Show that:


*

k k
c ψ ψ = < >

(7)

(Hint: multiply the starting equation from the left by ψ
n
* and use the
orthogonality of the basis set solutions ψ
n
).
Note: In a more careful treatment of this material, should be replaced by c
n
*
c
n
. There is no difference between the
two cases when c
n
is real, as will be the case in the examples we examine.
2
n
c

Applications to Molecular Orbitals
Let us suppose that we are trying to find approximate energies and wave functions for the butadiene p electrons. The
usual way of picturing this is shown in Figure 1 on the following page, where the (+) and (-) symbols indicate relative
phases. The four pictures are relatively easy to construct without any algebra, and the assignments to π and π
*

categories are also easy to rationalize. All four MO's also can be written in an algebraic way as:
MO n
n
c
n
ψ ψ =


where we take ψ
n
to be ψ
p
on carbon atoms 1 - 4 (n = 1,2,3,4).
When we construct molecular orbitals of this type, we are using a linear combination of atomic orbitals (LCAO)
approach. The goal of this approximate procedure is to determine, first, the best set of energy levels from the LCAO
mo's, and second, the shapes of the associated wavefunctions.



Figure 1. π Molecular Orbitals for Butadiene




Page 2
First let us look at energies. We begin with the first version of (6):
* *
*
*
m m n n m n m n m n mn
n n m n m n
m n mn
m n m n
m m n n m n
m n
n n
c c c c c c H
E
c c S
c c
c c
ψ ψ ψ ψ
ψ ψ
ψ ψ
| | | |
| |
\ . \ .
= = =
| || |
| |
\ .\ .
∑ ∑ ∑∑ ∑∑ ∫ ∫
∑∑
∑∑

∑ ∑

H H
(8)

where
*
mn m n
H ψ ψ =

H and S
*
mn m n
ψ ψ =

(9)

Our goal is, first of all, to find the minimum energy, which will be the best approximation to the correct E
o
. We can
ensure that <E> is minimized by taking its derivative with respect to a particular constant c
i
and setting it equal to 0:
2
2 2
0
m n mn n in n in n in n in
m n n n
i m n mn m n mn
m n m n
m n mn
m n
c c H c S c H c H E c S
E
c c c S c c S
c c S
| | | |

| |

\ . \ .
= = − =

| |
|
\ .
∑∑ ∑ ∑ ∑
∑∑ ∑∑
∑∑
2
n n

(10)

or: 0
n in n in
n n
c H E c S −
∑ ∑
= (11)

(which is usually written: 0
n in in
n n
c H E S

− =


∑ ∑
(12)

This equation must be true for all values of i. The set of all such equations is often expressed in matrix form:

11 11 12 12 13 13 1 1
21 21 22 22 23 23 2 2
31 31 32 32 33 33 3 3
1 1 2 2
....
....
....
....
....

j j
j j
j j
i i i i
H E S H E S H E S H E S
H E S H E S H E S H E S
H E S H E S H E S H E S
H E S H E S
− < > − < > − < > − < >
− < > − < > − < > − < >
− < > − < > − < > − < >
− < > − < >
1
2
3
3 3
0
0
0
... ...
... ...
0
....
i
i i ij ij
c
c
c
c
H E S H E S
| |
| | | |
|
| |
|
| |
|
| |
|
= | |
|
| |
|
| |
|
| |
| |
| |
− < > − < > \ . \ .
\ .
(13)

These equations are known collectively as the secular equations.

Some further simplifications:

1) Choose S
ij
= 1 if i = j, 0 if i =/ j

2) Call H
ij
= α if i = j (α is the energy of a non-bonding p orbital).

3) Call H
ij
= β if i = j +_ 1 (β is known as the resonance integral).

4) Take H
ij
= 0 for all other i,j combinations.


Problem: Show that α does indeed correspond approximately to the energy of a p orbital in a carbon atom.






Page 3
For butadiene, using these assumptions, the secular matrix equation becomes:

(14)
1
2
3
4
0 0
0 0
0 0
0 0
c E
c E
c E
c E
α β
β α β
β α β
β α
− | | | |
| |

|
=
|

| |
| |

\ .\ .
0
0
| |
|
| |
| |
|
|
\ .

where E = <E> has been used for notational simplicity. This equation can be simplified by dividing both sides by β and
then defining
E
x
α
β

= (Note that: E = α - βx)

When this is done, (14) reduces to: (16)
1
2
3
4
1 0 0 0
1 1 0
0 1 1 0
0 0 1 0
c x
c x
c x
c x
| | | |
| |
| |
=
| |
| |
| |
\ .\ .
0
| |
|
|
|
|
|
\ .

This equation is valid either if all the c
i
are 0 (a solution of no physical interest) or if the determinant of the square matrix
is 0. Solving this determinant leads to four values of x, which in turn leads to four values of E.

Solving the Determinant:

( ) ( )
3 2 4 2 2
1 0 0
1 0 1 1 0
1 1 0
1 1 1 0 1 1 3 1 3
0 1 1
0 1 0 1
0 0 1
x
x
x
1 x x x x x x x x x x y
x
x x
x
= − = − − − − = − + = − y + (17)
where y = x
2
. This has the roots:
3 5
2
y
±
= so
3 5
2
x
±
= = -1.618, -0.618, +0.618, +1.618 (18)
Problem: Write out the 4 energy values for E in terms of α and β using (15)

Note: MacDonald’s Theorem considers the relationship between the variational energy approximation for the nth E
level and the exact energy value for this level. The result is an extension of the variational theorem stated in (5) above:




n n exact
E E ≥ (cf. Pauling and Wilson, p. 188) (19)

The MO's associated with the energy values are derived by the following recipe:

1) put a particular x value into the secular determinant, e.g. x = -1.618:

1.618 1 0 0
1 1.618 1 0
0 1 1.618 1
0 0 1 1.6



− 18


2) write down the cofactors of each column in the determinant:


11 (1 1)
1.618 1 0
( 1) 1 1.618 1 1.000
0 1 1.618
A
+

= − − = −



Page 4
12 (1 2)
1 1 0
( 1) 0 1.618 1 1.618
0 1 1.618
A
+
= − − = −



13 (1 3)
1 1.618 0
( 1) 0 1 1 1.618
0 1 1.618
A
+

= − = −


14 (1 4)
1 1.618 1
( 1) 0 1 1.618 1.000
0 0 1
A
+

= − − = −

3) set
( )
1 1
4
2
1
1
2.690
i i
i
j
j
A A
c
A
=
= =

giving c
1
= 0.372 c
2
=0.601 c
3
= 0.601 c
4
= 0.372 (20)

Problem: Sketch a picture of the MO associated with these coefficients.

Problem: Derive the coefficients and pictures for the other three MO's

Problem: Show that the first MO is normalized.

Problem: Show that
2 2 2 2
11 12 13 14
1 c c c c + + + =
where "11" refers to the coefficient for the first MO for carbon 1, "12" is the coefficient for the second MO for
carbon 1, etc.


More complex problems and computer codes

It is impractical to work out solutions "by hand" for matrix problems with a dimension greater than 4, and so we turn to
computer programs to solve matrix equations analogous to (16). There is a good discussion of the general method
("Jacobi rotation") in the J. Chem. Source cited at the beginning of this unit, and also in a programming source such as
"Numerical Recipies" by Press, et al. The procedures generally transform the square matrix of (16), with x set equal to
zero, by a series of Jacobi rotations into a diagonal form (that is, a set of transformations that makes all off-diagonal
elements arbitrarily close to zero). When the square matrix of (16) is "diagonalized" in this way, the diagonal elements
constitute the set of "x" eigenvalues, and the product of all the successive Jacobian rotation matrices is a square matrix
with the property that each row (or column) contains the set of LCAO coefficients. We have a FORTRAN
implementation of this procedure.

Applications of the simple HMO method

1) the 4n + 2 rule (cf. Streitweiser, MO Theory for Organic Chemists)

2) epr spectra for conjugated radical anions and cations of conjugated systems. We will do some spreadsheet examples.











Page 5
B. Approximate Solutions - Perturbation Theory

Perturbation theory is an alternative rather useful way of getting approximate results for complex problems in quantum
mechanics. It is developed as follows:

Assume that the Hamiltonian operator can be broken up into two parts: v
o
λ = + H H (21)

where

is the Hamiltonian for an exactly solvable problem and v is an additional potential energy term (a small one
we hope!) which makes the problem difficult or impossible to solve exactly.
0
H

We then assume that the eigenfunctions of can be written in the following form: H

(1) 2 (2) 3 (3)
...
o
ψ ψ λψ λ ψ λ ψ = + + + +

(22)

and that (23)

(1) 2 (2) 3 (3)
...
o
E E E E E λ λ λ = + + + +
The
o
ψ and are solutions to the exact problem (v = 0).
o
E
(1)
ψ and are known as first-order perturbations,
(1)
E
(2)
ψ and
are second order perturbations, etc.. The theory is useful in cases where the series terms quickly get vanishingly
small. We also usually assume that λ = 1 for practical calculations, but we do not want to do this just yet. Now consider
the correct SE:
(2)
E
E ψ ψ =

H

which becomes, with substitution:
( )
( )
(1) 2 (2) 3 (3)
(1) 2 (2) 3 (3) (1) 2 (2) 3 (3)
v ...
... ... 0
o o
o o
E E E E
λ ψ λψ λ ψ λ ψ
λ λ λ ψ λψ λ ψ λ ψ
+ + + + +

− + + + + + + + + =

H
(24)
The game we play now involves collecting like terms in λ in the products of (24):

( )
( )
( ) ( ) ( )
| |
1) (1) (1)
1 1 2 2 (1) (2) (2)
3
v
v
... ... 0
o o o o o o o o
o o
E E E
E E E
ψ ψ λ ψ ψ ψ ψ
o
λ ψ ψ ψ ψ ψ
λ

− + + − −

+ + − − −

+ + =
H H
H

)
(25)
Then, since λ is a variable, we require the coefficient of each λ term to = 0 (we encountered this property earlier in the
term with the harmonic oscillator problem). This allows us to determine, in succession,
(1) (1) (2) (2
, , , E E ψ ψ etc.

(1)
E : Setting the coefficient of λ in (25) equal to 0 gives:
(1) (1) (1)
v
o o o o
E E ψ ψ ψ ψ 0 + − − H =
E
(26)

Rearrange this to:
(1) (1) (1)
v
o o o o
E ψ ψ ψ ψ = + − H (27)

and then multiplying both sides by
* o
ψ from the left and integrating over all space gives:

* (1) (1) * * * (1) * (1)
= v
o o o o o o o o o o
E E E ψ ψ ψ ψ ψ ψ ψ ψ ψ ψ = + − H (28)

There is a property of wavefunctions which we have not introduced or explored known as the Hermitian property
which is stated as follows:

*
* *
a b b a
ψ ψ ψ ψ = H H (29)
We can use this property to eliminate the last two terms:

(1) * * (1)* (1)* * *
= v v 0 v
o o o o o o o o o o o o
E E ψ ψ ψ ψ ψ ψ ψ ψ ψ ψ ψ ψ + − = − = H (30)
so:
*
(1) *
*
v
v
o o
o o
o o
ψ ψ
E ψ ψ
ψ ψ
= = assuming normalization of
o
ψ . (31)
Page 6

(1)
m
ψ : for a particular energy level E
m

(1)
m
ψ is most often treated as a linear
combination of the exact solutions:
(1) o
m nm
n
c
n
ψ ψ =

(32)

If we look at equation (26) and focus on the middle terms, both of which involve
(1)
m
ψ it is easy to show that if

(1')
m
ψ is a solution to (26), then
(1) (1') o
m m
a
m
ψ ψ ψ = + will be an equally good solution.

Problem: Prove that this claim is true.

In other words,
(1)
m
ψ is not determined exactly by (26). We can take advantage of this by noting that:


(1)* (1')* *
=
o o o o
m m m m m m
a ψ ψ ψ ψ ψ ψ 0 + = (33)

if we choose the arbitrary constant as:
(1)* (1')*
*
o o
m m m m
o o
m m
a
ψ ψ ψ ψ
ψ ψ

= (34)

This means that in general we can assume that
(1)
m
ψ will be chosen so that it is orthogonal to
o
m
ψ .

Let us now go back to (32) and solve it for c
mn
:
First we note that the orthogonality of
(1)
m
ψ and
o
m
ψ now requires c
mm
= 0.

Problem: Show that if c
mm
= 0 then
(1)
m
ψ and
o
m
ψ are in fact orthogonal.

Let us now plug (32) into (26). This leads to a formula for the c
mn
coefficients as follows:

vψ ψ (35)

( )
(1)
(1)
(1)
v
v
o o o o
m mn n m mn n m m
o o o o o
m mn n n m mn n m m
o o o o o
m mn n m n m m
c E c E
c E E c E
c E E E
ψ ψ ψ
ψ
ψ ψ ψ
+ − −
+ − −
+ − −
∑ ∑
∑ ∑

H
o
o
ψ
ψ
=
=
o
which rearranges to:
( )
(1)
v
o o o o
mn m n n m m m
c E E E ψ ψ − = −

ψ (36)

To get a particular coefficient c
mk
, multiply both sides of (36) by
o
k
ψ and integrate
over all space. Taking advantage of the orthogonality of the
o
n
ψ functions, we get:

( ) ( )
* * (1) *
v
o o o o o o o o o o o o
mn m n k n mk m n k n m k n k n
c E E c E E E
*
v ψ ψ ψ ψ ψ ψ − = − = − =

ψ ψ (37)

and solving for c
mk
thus gives:
( )
*
v
o o
k m
mk
o o
m k
c
E E
ψ ψ
=

(38)
Finally, this gives an explicit formula for
(1)
m
ψ
( )
*
(1)
v
o o
n m
o
m
o o
n
m n
E E
ψ ψ
n
ψ ψ

=



(39)
(2)
E : Setting the coefficient of λ
2
= 0, we multiply by
* o
ψ once again from the left, followed by
integration. The Hermitian property is now used to eliminate the second and third terms in the
λ
2
coefficient in (25), giving:
Page 7
* (1) (1) * (1) * (1)
(2)
*
v v
o o o
o o o o
E
E
ψ ψ ψ ψ ψ ψ
ψ ψ ψ ψ

=
*
= (40)

Problem: Show the steps in the derivation of (40). (Orthogonality accounts for the numerator
simplification.)

If
(1)
ψ is written as an expansion once more (cf. (32)), equation (40) can be written as:


( )
2
* (1) * *
(2)
* *
v v v
o o o o
m m m mn n m n
o o o o o o
n
m m m m m n
c
E
E E
ψ ψ ψ ψ ψ ψ
ψ ψ ψ ψ
o


= = =





(41)

Again, normalization of the
o
m
ψ values has been assumed.

Applications:
1. Perturbed Harmonic Oscillator
2. Electronic transitions: e.g. IR spectroscopy of HCl
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and second. the best set of energy levels from the LCAO mo's. where the (+) and (-) symbols indicate relative phases.4 (n = 1. All four MO's also can be written in an algebraic way as: ∼ ψ = cψ where we take ψ to be ψ on carbon atoms 1 . exact cn ≥ 0  Hence. MO ∑ n n n n p When we construct molecular orbitals of this type. Show that: * ∼ ck = < ψ k ψ > (7) (Hint: multiply the starting equation from the left by ψn* and use the orthogonality of the basis set solutions ψn ). The usual way of picturing this is shown in Figure 1 on the following page.4). π Molecular Orbitals for Butadiene Page 2 . 2 Note: In a more careful treatment of this material. Prove that all the steps in (6) are correct. we are using a linear combination of atomic orbitals (LCAO) approach. Applications to Molecular Orbitals Let us suppose that we are trying to find approximate energies and wave functions for the butadiene p electrons.3.exact QED. and the assignments to π and π* categories are also easy to rationalize. _ ∑c 2 n 2 = ∑ En cn where we have assumed that the approximate energy will be an Problem 1.which can be rearranged to: Eo 2 2    approximation to the lowest E level. as will be the case in the examples we examine. the shapes of the associated wavefunctions. ∼ Problem 2: The substitution: ψ = ∑ cnψ n is reasonable if it is a general way of n describing any possible approximate wave function. Consider now:  Eo − Eo .2. We can prove that this is the case by showing how to obtain a general formula for ck. <Eo> > Eo. The four pictures are relatively easy to construct without any algebra. first.exact  ∑ cn = ∑  En − Eo. Figure 1. There is no difference between the two cases when cn is real. The goal of this approximate procedure is to determine. cn should be replaced by cn*cn.

.   . H 3 j − < E > S3 j   c3   0    =     . Page 3 . The set of all such equations is often expressed in matrix form:  H11 − < E > S11   H 21 − < E > S21 H − < E > S 31  31  . Problem: Show that α does indeed correspond approximately to the energy of a p orbital in a carbon atom.... to find the minimum energy..First let us look at energies... H − < E > S i1  i1 H12 − < E > S12 H13 − < E > S13 ..   . We begin with the first version of (6):     H  ∑ cnψ n  n   n = E =   *  ∫  ∑ cmψ m   ∑ cnψ n   n  n  ∫∑c ψ  m  * m ∑∑ c c ∫ψ H ψ ∑∑ c c ∫ψ ψ m n * m m n m n * m n m n n ∑∑ c c H = ∑∑ c c S m n m n m n m n mn (8) mn where * * H mn = ∫ψ mH ψ n and S mn = ∫ψ mψ n (9) Our goal is..... which will be the best approximation to the correct Eo. 0 if i = j / 2) Call Hij = α if i = j (α is the energy of a non-bonding p orbital)..        . _ 3) Call Hij = β if i = j + 1 (β is known as the resonance integral).....   .    H i 2 − < E > Si 2 H i 3 − < E > Si 3 .... H 2 j − < E > S 2 j   c2   0      H 32 − < E > S32 H 33 − < E > S33 ..... 4) Take Hij = 0 for all other i. first of all. We can ensure that <E> is minimized by taking its derivative with respect to a particular constant ci and setting it equal to 0: ∂ E ∂ci =0= 2∑ cn H in n ∑∑ c m n n in m n c Smn      ∑∑ cm cn H mn  2  ∑ cn Sin  ∑ cn H in − E ∑ cn Sin  m n   n =2 n n − 2 ∑∑ cm cn Smn   m n  ∑∑ cm cn S mn   m n  n in (10) or: ∑c H n − E ∑c S n =0 (11)  =0  (which is usually written: ∑c n n   H in − E  ∑S n in (12) This equation must be true for all values of i. H ij − < E > Sij   ci   0    (13) These equations are known collectively as the secular equations. H1 j − < E > S1 j   c1   0   H 22 − < E > S 22 H 23 − < E > S23 ...j combinations. Some further simplifications: 1) Choose Sij = 1 if i = j.

618: −1. Solving the Determinant: x 1 0 0 1 x 1 0 0 1 x 1 x 0 0 1 x 1 0 =x1 0 1 x 1 1 0 0 1 x x 1 − 1 0 x 1 = x ( x3 − x − x ) − ( x 2 − 1) = x 4 − 3 x 2 + 1 = y 2 − 3 y + 1 (17) where y = x2. (14) reduces to: x  1 0  0  1 0 0   c1   0      x 1 0   c2   0  = 1 x 1   c3   0      0 1 x  c4   0      (16) This equation is valid either if all the ci are 0 (a solution of no physical interest) or if the determinant of the square matrix is 0. -0. The result is an extension of the variational theorem stated in (5) above: En ≥ En exact (cf.618 2 2 Problem: Write out the 4 energy values for E in terms of α and β using (15) (18) Note: MacDonald’s Theorem considers the relationship between the variational energy approximation for the nth E level and the exact energy value for this level. using these assumptions. p.g.000 1 0 Page 4 .618 1 −1. This has the roots: y = 3± 5 3± 5 so x = = -1. Pauling and Wilson.618 1 0 0 1 0 0 1 0 0 1 −1.618 1 0 1 −1.618.618 2) write down the cofactors of each column in the determinant: −1. the secular matrix equation becomes: β 0 0   c1   0  α − E      0   c2   0  α−E β  β =  0 β α−E β   c3   0        0 0 β α − E   c4   0       (14) where E = <E> has been used for notational simplicity.βx) then defining =x β When this is done. +1.618.618 1 −1. +0.618.For butadiene. This equation can be simplified by dividing both sides by β and α−E (Note that: E = α . which in turn leads to four values of E.618 = −1. e. Solving this determinant leads to four values of x. 188) (19) The MO's associated with the energy values are derived by the following recipe: 1) put a particular x value into the secular determinant.618 A = (−1) 11 (1+1) 1 −1. x = -1.

There is a good discussion of the general method ("Jacobi rotation") in the J.618 0 1 −1. Applications of the simple HMO method 1) the 4n + 2 rule (cf.1 0 1 1 0 1 −1. We will do some spreadsheet examples. Streitweiser. and the product of all the successive Jacobian rotation matrices is a square matrix with the property that each row (or column) contains the set of LCAO coefficients.372 (20) 1j 2 Problem: Sketch a picture of the MO associated with these coefficients. Source cited at the beginning of this unit. the diagonal elements constitute the set of "x" eigenvalues.601 c4 = 0. MO Theory for Organic Chemists) 2) epr spectra for conjugated radical anions and cations of conjugated systems. Chem.601 c3 = 0. etc. The procedures generally transform the square matrix of (16).618 A12 = (−1)(1+ 2) 0 −1.690 1 −1.618 A = (−1) 13 (1+ 3) 0 0 1 1 1 0 = A1i 2. and so we turn to computer programs to solve matrix equations analogous to (16). a set of transformations that makes all off-diagonal elements arbitrarily close to zero). with x set equal to zero. et al. When the square matrix of (16) is "diagonalized" in this way.618 1 −1. by a series of Jacobi rotations into a diagonal form (that is. Problem: Derive the coefficients and pictures for the other three MO's Problem: Show that the first MO is normalized. 2 2 2 2 Problem: Show that c11 + c12 + c13 + c14 = 1 where "11" refers to the coefficient for the first MO for carbon 1. More complex problems and computer codes It is impractical to work out solutions "by hand" for matrix problems with a dimension greater than 4. and also in a programming source such as "Numerical Recipies" by Press.618 = −1.618 1 −1. Page 5 .372 c2 =0.000 1 = −1.618 A = (−1) 14 (1+ 4) 0 0 3) set ci = A1i ∑( A ) j =1 4 giving c1 = 0. We have a FORTRAN implementation of this procedure.618 = −1. "12" is the coefficient for the second MO for carbon 1.

Now consider the correct SE: ∼ ∼ H ψ = Eψ which becomes.. The ψ o and E o are solutions to the exact problem (v = 0).. with substitution: (H + λ v ) ψ + λψ  − ( E + λE + λ E o o o (1) 2 (1) (2) + λ 3 E (3) + .ψ (1) . ψ (2) and E (2) are second order perturbations. The theory is useful in cases where the series terms quickly get vanishingly small. = 0    + λ 2ψ (2) + λ 3ψ (3) + . but we do not want to do this just yet.... This allows us to determine. ) ψ o + λψ (1) + λ 2ψ (2) + λ 3ψ (3) + . We then assume that the eigenfunctions of H can be written in the following form: ∼ ψ = ψ o + λψ (1) + λ 2ψ (2) + λ 3ψ (3) + . E (1) ..... since λ is a variable. It is developed as follows: Assume that the Hamiltonian operator can be broken up into two parts: H = H o + λv (21) where H 0 is the Hamiltonian for an exactly solvable problem and v is an additional potential energy term (a small one we hope!) which makes the problem difficult or impossible to solve exactly.] + . (24) The game we play now involves collecting like terms in λ in the products of (24): (H o ψ o − E oψ o ) + λ  vψ o + H oψ (1) − E oψ (1) − E (1))ψ o    1 1 2 + λ 2  vψ (1) + H oψ (2) − E oψ (2) − E ( )ψ ( ) − E ( )ψ o    + λ 3 [.. Approximate Solutions .. (22) (23) and that E = E o + λ E (1) + λ 2 E (2) + λ 3 E (3) + ... Page 6 .. E (2) . = 0 (25) Then.B. ψ (1) and E (1) are known as first-order perturbations..ψ (2 ) etc. we require the coefficient of each λ term to = 0 (we encountered this property earlier in the term with the harmonic oscillator problem). E (1) : Setting the coefficient of λ in (25) equal to 0 gives: vψ o + H oψ (1) − E oψ (1) − E (1)ψ o = 0 (26) (27) Rearrange this to: E (1)ψ o = vψ o + H oψ (1) − E oψ (1) and then multiplying both sides by ψ o* from the left and integrating over all space gives: ψ o* E (1)ψ o = E (1) ψ o*ψ o = ψ o* vψ o + ψ o*H oψ (1) − ψ o* E oψ (1) (28) There is a property of wavefunctions which we have not introduced or explored known as the Hermitian property which is stated as follows: * * ψ aH ψ b = ψ b H ψ a * (29) We can use this property to eliminate the last two terms: E (1) ψ o*ψ o = ψ o* vψ o + ψ (1)*H oψ o − ψ (1)* E oψ o = ψ o* vψ o − 0 = ψ o* vψ o (30) (31) so: E (1) = ψ vψ o* o ψ o*ψ o = ψ o* vψ o assuming normalization of ψ o .Perturbation Theory Perturbation theory is an alternative rather useful way of getting approximate results for complex problems in quantum mechanics. in succession. etc. We also usually assume that λ = 1 for practical calculations.

we get: ∑c (E mn o m o o o o o (1) o o − En ) ψ ko*ψ n = cmk ( Em − En ) = ψ ko* vψ n − Em ψ ko*ψ n = ψ ko* vψ n (37) and solving for cmk thus gives: cmk = (E o ψ ko* vψ m o m − Eko ) (38) o o  ψ n * vψ m  o  ψn o o n  ( E m − En )    (2) 2 o* E : Setting the coefficient of λ = 0. (1) o Problem: Show that if cmm = 0 then ψ m and ψ m are in fact orthogonal. Problem: Prove that this claim is true. this gives an explicit formula for ψ m (1) ψm = ∑  (39) Page 7 . Taking advantage of the orthogonality of the ψ n functions. Let us now plug (32) into (26). The Hermitian property is now used to eliminate the second and third terms in the λ2 coefficient in (25). followed by integration. then ψ m = ψ m + aψ m will be an equally good solution. we multiply by ψ once again from the left. multiply both sides of (36) by ψ ko and integrate o over all space.(1) (1) ψ m : for a particular energy level Em ψ m is most often treated as a linear (1) o combination of the exact solutions: ψ m = ∑ cnmψ n (32) n (1) If we look at equation (26) and focus on the middle terms. both of which involve ψ m it is easy to show that if (1') (1) (1') o ψ m is a solution to (26). (1) In other words. giving: (1) Finally. This leads to a formula for the cmn coefficients as follows: o o o o (1) o vψ m + ∑ cmnH ψ n − Em ∑ cmnψ n − Em ψ m = o o o o o (1) o vψ m + ∑ cmn Enψ n − Em ∑ cmnψ n − Em ψ m = o o o o (1) o vψ m + ∑ cmn ( En − Em )ψ n − Em ψ m (35) which rearranges to: ∑c (E mn o m o o o (1) o − En )ψ n = vψ m − Em ψ m (36) To get a particular coefficient cmk. Let us now go back to (32) and solve it for cmn: (1) o First we note that the orthogonality of ψ m and ψ m now requires cmm = 0. We can take advantage of this by noting that: (1)* o (1')* o o o ψ m ψ m = ψ m ψ m + a ψ m*ψ m = 0 (33) if we choose the arbitrary constant as: a = (1)* o (1')* o ψm ψm − ψm ψm o o ψ m*ψ m (34) (1) o This means that in general we can assume that ψ m will be chosen so that it is orthogonal to ψ m . ψ m is not determined exactly by (26).

normalization of the ψ m values has been assumed. Applications: 1. Electronic transitions: e. (Orthogonality accounts for the numerator simplification.) If ψ (1) is written as an expansion once more (cf. Perturbed Harmonic Oscillator 2. equation (40) can be written as: o (1) ψ m* vψ m o o ψ m*ψ m o o ψ m* v∑ cmnψ n o o ψ m*ψ m E (2) = =  ψ o* vψ o 2  m n  = ∑ o o  ( E m − En )  n   (41) o Again.g. IR spectroscopy of HCl Page 8 .E (2) = ψ o* vψ (1) − E (1) ψ o*ψ (1) ψ o*ψ o = ψ o* vψ (1) ψ o*ψ o (40) Problem: Show the steps in the derivation of (40). (32)).

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