Bonding in H2+: MO

Theory
Jan. 28, 2014

H2+ is the simplest molecular species

The Hamiltonian is
2
2
2
2
= p e e + e
H
2m rA rB
R
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Class 10

Approx. wavefunction for H2+

guessed from R =
Two equally likely dissociation pathways for H2 +
1

H2 + HA + HB +

H2 + HB + HA +

When R = , has significant amplitude only near A and

near B
1

Electron near A = = cA 1sA

Electron near B = = cB 1sB

Guess that = cA 1sA + cB 1sB everywhere in space

Matter wave constructed by superposition of H AO

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Indistinguishability restricts cA and cB

Physically measurable quantities unaffected on interchanging
particle labels
||2 is unaffected by particle interchange

|(A, B)|2 = |(B, A)|2

= |cA |2 = |cB |2 = |c|2
For real values, cA = cB and cA = cB or

= c(1sA 1sB )

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Normalization used to find c.

Z

|1sA 1sB |2 d
Z
Z
Z
Z
2
|1sA |2 d 1sA 1sB d 1sA 1sB d + |1sB |2 d
1=c

|| d = c

When R ,
Z

1sA 1sB d

Z
=

1sA 1sB d = 0.

1 = c2 (1 + 0 + 0 + 1)

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At infinite internuclear distance

E(H+
2 ) = EH (1s)
Z

Hd

E() =
all space

1s(A) 1s(A)
HA d
2
2
near A
Z
1s(B) 1s(B)
HB d
+
2
2
near B
1
1
= EH (1s) + EH (1s) = EH (1s)
2
2
Z

Define this as the zero of energy

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At finite R, is approximately a sum

of atomic orbitals
+ = c0 (1s(A) + 1s(B))
= c1 (1s(A) 1s(B))
Linear Combination of Atomic Orbitals (LCAO)
1

Maximum simplicity with reasonable accuracy

Natural and intuitive appeal

Simplifies calculations - atomic orbitals already determined

to high accuracy

Wavefunctions around atoms in molecules like those

around free atoms

Bond formation a small perturbation to atomic structure

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Normalization constant depends on

the overlap integral
Z

|+ | d = 1 =

Defining S =

c20

Z

|1s(B)|2 d

Z
Z
+ 1s(A) 1s(B)d + 1s(A)1s(B) d
|1s(A)| +

1s(A) 1s(B)d , we find

|+ |2 d = 2c20 (1 + S)

S is zero when A and B

are infinitely far apart

S has a large contribution

from regions where 1s(A)

and 1s(B) are both
appreciable
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Electron density between the nuclei is

more in +
The electron density in the + MO is
|+ |2 =

|1s(A)|2 + |1s(B)|2 + 2(1s(A)1s(B))

2(1 + S)

S reduces the electron density everywhere.

Between the nuclei 2(1s(A)1s(B)) is dominant and
= |+ |2 > |1s(A)|2 + |1s(B)|2
Constructive interference of the two atomic orbitals between the
nuclei in + .

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There are 0 and 1 nodes in the two

lowest MOs

Dotted - non-interacting,
dashed - LCAO, solid - exact
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Two lowest MOs show interference

Bonding MO

Antibonding MO

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Forces responsible for binding

Potential energy - electrostatic
Kinetic energy - delocalization

+ describes a bonding state

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The approximate
energy of + is
R
given by +H+d
1
E+ (R) =
2(1 + S)

Z
Z

1s(A)H1s(A)d + 1s(A)H1s(B)d +

Z
1s(B)H1s(A)d + 1s(B)H1s(B)d

Define an integral
Z
Hij =
E+ (R) =

i Hj d

HAA + HAB + HBA + HBB

2(1 + S)

E+ (R) =
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HAA + HAB
(1 + S)
Class 10

The atomic integral HAA has a

Coulomb term

Z
p2
e2
e2
=
1s(A)

1s(A)d +
1s(A)1s(A)d
2m rA
R
Z
e2
1s(A) 1s(A) d
rB
2
e
= EH (1s) +
+J
R
Z

HAA

where

Z
J =

e2
1s(A) 1s(A)d
rB

is the Coulombic interaction between the orbital around one

atom and the other nucleus.
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The resonance integral HAB has an

exchange term

Z
p2
e2
e2
=
1s(A)

1s(B)d +
1s(A)1s(B)d
2m rB
R
Z
e2
1s(A) 1s(B) d
r

 A
2
e
= S EH (1s) +
+K
R
Z

HAB

where

Z
K=

e2
1s(A) 1s(B)d
rA

has no classical interpretation.

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In the GS the electron has a net

bonding effect

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Exchange integral is important for

binding

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The LCAO method can be

generalized
If = c1 f1 + c2 f2 then E =
E(c1 , c2 ) =

Hd is

c21 H11 + 2c1 c2 H12 + c22 H22

c21 S11 + 2c1 c2 S12 + c22 S22

At the minimum of the energy

E
E
=
=0
c1
c2
c1 (H11 ES11 ) + c2 (H12 ES12 ) = 0
c1 (H21 ES21 ) + c2 (H22 ES22 ) = 0

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The LCAO method can be extended

If =

R
then E = Hd is
P 2
P P
2ci cj Hij
i ci Hii +
Pi Pj>i
E(c1 , c2 ) = P 2
i ci Sii +
i
j>i 2ci cj Sij

i ci fi

At the minimum of the energy

E
=0
ci
c1 (H11 ES11 ) + c2 (H12 ES12 ) + = 0
c1 (H21 ES21 ) + c2 (H22 ES22 ) + = 0

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