Chemistry 431

Lecture 10 Diatomic molecules

Born-Oppenheimer approximation LCAO MO application LCAO-MO li ti t to H2+ The potential energy surface MOs for diatomic molecules

NC State University

Born-Oppenheimer Born Oppenheimer approximation

Molecular motion includes the motion of both nuclei and electrons. The time scale of the motion of the nuclei is orders of magnitude slower than electron motion due to the difference in mass:

m e = 9.109 x 10 kg 27 m p = 1.672 x 10 kg

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The potential energy surface

The idea that nuclear and electronic motions can be separated p implies p that there is a nuclear potential energy surface U(R) ( ) where R is the internuclear distance. The potential surface has an equilibrium geometry Re and well depth De.

Hydrogen molecule ion wave functions

The spatial wavefunction on each of two H atoms forms linear combinations: -

H1sA

or 1sA

rA

rB R

H1sB

or 1sB

The atomic wave functions form linear combinations to make molecular orbital wave functions.

Y = 1sA 1sB

The hamiltonian for H2+

The potential involves three particles, one electrons and two protons. In atomic units it is given by

V = r1 + r1 + 1 R A B
The hamiltonian includes the kinetic energy terms for the electron only since the Born-Oppenheimer approximation allows separation of nuclear and electronic motion. The i t internuclear l di distance t Ri is fi fixed d and d th the nuclear l ki kinetic ti energy is zero.
2 1 H = +V 2

Setting up the energy calculation l l ti f for H2+

The energy gy is obtained by y evaluating g the expectation value: * H d The denominator E = gives the required *d normalization.
* d =
=

1s A +1s B 1s A +1s B d
* *
*

1s A 1s Ad +
*

1s A1s Bd +
*

1s B1s Bd +
*

1s B1s Ad
*

1 + S + 1 + S , where

1s A1s Ad = 1 and

1s A1s Bd = S
*

Significance of the overlap integral

The wave functions 1sA and 1sB are not orthogonal since they are centered on different nuclei. The overlap integral S is a function of the internuclear distance.
A B

Overlap region

Normalized LCAO wave functions

The LCAO wave functions for the H2+ molecule ion are

+=
and

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

1 = 1sA 1sB 2(1 S)

These wave functions are orthogonal as well as normalized. li d

Energy levels in H2+

Explicit substitution of the hamiltonian gives
E=

* H d =
=

1 1 + 1 1 2 r rB R 2 A

1s A
*

1 1 + 1 1 2 r rB R 2 A

1s Ad

1s A
*

1 1 + 1 1 2 r rB R 2 A

1s Bd

+ +

1s 1s

1 1 + 1 1 2 r rB R B 2 A

1s Bd 1s Ad

1 1 + 1 1 2 r rB R B 2 A

Energy levels in H2+

= +

1s A
*

1 E 1s r1B + R 1 E 1s r1A + R

1s Ad + 1s Bd +

1s A
*

1 E 1s r1B + R 1 E 1s r1B + R

1s Bd 1s Ad

1s B
*

1s B
*

Since
1 1 2 r 2 A 1 1 2 r 2 B

1s A =E 1s1s A 1s B =E 1s1s B

Energy gy levels in H2
= E1s 1+S + 1s A
*

+
1s Bd

1 +1 r B R

1s Ad +

1s A
*

1 +1 r B R

+ E 1s 1+S +

1s B
*

r1 + 1 A R

1s Bd +

1s B
*

r1 + 1 B R

1s Ad

To further evaluate these integrals we define the Coulomb integral 1 s A1s A 1 1 1 d + J = 1s A r + R 1s Ad = rB R

* * B

And the exchange integral

K = 1s B
*

1 +1 r
B

= R 1s Ad

1s B1s A
*

rB

d + S R

Energy levels in H2+

= E+

* +

H +d
*

+d

E1s2 1 + S + 2 J + K 2 1+S

=E + J + K E+ 1s 1 + S
= E

H d
*

E1s2 1 S + 2 J K 2 1S

J K E = E 1s + 1S

Diagram of H2+ energy levels

J K 1S
anti-bonding

E1s

E1s

bonding

J +K 1+S
Note that the anti-bonding anti bonding level is more destabilizing than the bonding level is stabilizing.

Potential energy gy surface for H2+

Using elliptical integrals that S, J, and K integrals can be solved analytically y y to yield y
S ( R) = e R
2 R 1+R+ 3

J ( R) = e 2 R 1 + 1 R

K ( R) = S e R 1+ R R

MO treatment of H2
anti-bonding

E1s

E1s 1

bonding

The two Th t electrons l t must t have h opposite it spins,a i and db b. The wave function must be anti-symmetric with respect to electron exchange exchange.

MO = b(1) b(2)

Spatial part

1 (1)(2) (2)(1) 2 Spin part (anti-symmetric)

Application to diatomic molecules

2pz 2px,y 4 2 3 1 2 1

Li2

Be2

B2

C2

N2

O2

F2

2s

Considering only valence electrons we

can fill the molecular orbitals of diatomics. diatomics Linear combinations of 2s, 2pz give s orbitals. Linear combinations of 2px,y give p orbitals. The Th relative l ti energy ordering d i d depends d on th the number of electrons in occupied orbitals.

Molecular Orbital Theory

In MO theory electrons are treated as including the entire molecule.
Each MO is built up from a linear combination of atomic i orbitals bi l (LCAO) (LCAO).

MO = i c ii where i are atomic orbitals =1

I

The coefficients are optimized by the selfconsistent i t t field fi ld (SCF) method. th d The variational principle justifies minimization of gy by y adjustment j of the coefficients ci. the energy

Nitrogen Molecular Orbitals

Example p of a Homonuclear Diatomic

Isosurfaces represent * of orbital showing 90% of total probability. The spatial wavefunction is an LCAO LCAO. Core electrons are not included. There are five electrons for each N atom.

Dinitrogen 1 MO

N2 2* MO

N2 1 MO

This is Thi i a doubly d bl degenerate d t orbital. bit l Only one of the two is shown.

N2 3 MO

N2 2* MO

This is Thi i a doubly d bl degenerate d t orbital. bit l Only one of the two is shown.

N2 4* MO

Energy level diagram for N2

Negative energies represent bonding interactions (< 0 eV) For N2 all there are t electrons ten l t so all ll orbitals are filled through 3 Only valence orbitals are shown
4 1

3 1 2 1 1

Molecular Properties
Bond length (structure). Vibrational frequency: q y
Calculated at stationary point. Depends p on accuracy y of second derivative matrix with respect to nuclear displacement.

Dipole Di l moment t( (clearly l l zero f for N2). ) Absorption spectrum.