Valence Bond Theory

Born Oppenheimer Approximation

2 Pei Te = i = 12me n

The Hamiltonian for a molecule of N atoms and n electrons

Can be written as H = TN + Te + VNe + Vee + VNN

TN =
j = 1 2mj

2 PNj

TN : Kinetic energy of all nuclei

Te : Kinetic energy of all electrons VNe : Electron - nuclei attraction

VNe
Vee

eZNk = i k | RNk ri |

1 n N e2 = 2 i k i| rk ri |

Vee : Electron - electron repulsion VNN : Nucleus - nucleus repulsion

VNe

1 N N ZNiZNk = 2 i k i| RNk ri |

Valence Bond Theory

Born Oppenheimer Approximation

The solutions to the Schrdinger equation are written as H(RN;re )(RN;re ) = E(RN;re ) In the Born - Oppenheimer approximation we fix the nuclei in space and solve : {H - TN } (re ) = He (re ) = Ee (re ) Both E and will depend on at r what geometry (RN ) we fixed the nuclei Thus both E and depends on the parameter RN
We can thus write He (re , RN ) (re , RN ) = Ee (RN ) (re , RN )

Remove kinetic energy of nuclei

Valence Bond Theory

Born Oppenheimer Approximation

The term Ee (RN ) reresents the energy of molecule as a function of the nuclear positions.
It is also referred to as the potential energy surface Ee (RN )
Potential energy surface for diatomic molecule as function of internuclear distance

A molecular potential energy curve. The equilibrium bond length corresponds to the energy minimum.

Valence Bond Theory

Born Oppenheimer Approximation

The function Ee (RN ) is the potential energy for the nuclei.

Hence we can find the wavefunction for the motion of the nuclei from the Schrdinger equation
{TN + Ee (RN )}(RN ) = vib (RN )

The total wavefunction becomes to a good approximation (RN;re ) = (RN;re )(RN )

And the total energy E = Ee + vib

Valence Bond Theory Born Oppenheimer Approximation It is possible to solve For a diatomics we get {TN + E(RN )}(RN ) = vib (RN ) dE E(RN ) = E(Re ) + ( ) Re approximately dR R =R e by expanding EN (RN ) in a Taylor series 1 d2E 1 d3E + ( 2 ) Re 2 + ( 3 ) Re 3 + ... around the equilibrium 2 dR 8 dR R =R e R =R e structure E(Re ) : dissociation energy De ( dE ) = 0 at equilibrium dR R =R e Re = RN Re : Deviation from equilibrium d2E ( 2 ) : Force constant KR dR R =R
e

d3E ( 3) dR

:
R =R e

Higher terms

Valence Bond Theory Born Oppenheimer Approximation We can thus write 1 {TN + KR Re 2 E(RN )}(RN ) 1 2 E(RN ) = E(Re ) + KR Re 2 2 = (' vib )(RN ) is the equation for the harmonic And the equation {T + E(R )}(R ) = (R ) oscillator
N N N N

reduces to

1 {TN + KR Re 2 E(RN )}(RN ) 2 = ( vib E(Re ))(RN )

= ' vib (RN )

Valence Bond Theory

Born Oppenheimer Approximation 1 {TN + KR Re 2 E(RN )}(RN ) 2

= (' vib )(RN ) is the equation for the harmonic oscillator
1 E = h( + v ) v = 0,1, 2, 3, 4, 5, 6, 7 2
k = m

Valence Bond Theory

Born Oppenheimer Approximation 1 {TN + KR Re 2 E(RN )}(RN ) 2

= (' vib )(RN ) is the equation for the harmonic oscillator
1 E = h( + v ) v = 0,1, 2, 3, 4, 5, 6, 7 2
k = m
v (x) = 1
1 2 2 v v!

y2 exp Hv ( y ) 2

What you should learn from this lecture

Be able to identify the different terms in the Hamiltonian for a molecule of N atoms and n electrons given by H = TN + Te + VNe + Vee + VNN Understand qualitative what the potential energy curve Ee (R N ) of a molecule represents and what approximation is involved in obtaining it from H e (re , R N ) (re , R N ) = E e (R N ) (re , R N ) You are not asked to derive the Born - Oppenheimer approximation. However you should know that it involves writing the total wavefunction as a product of the electronic wavefunction (R N ;re ) and the nuclear wavefunction (R N ) (R N ;re ) = (R N ;re )(R N )

You should be aware that the nuclear wavefunction can be obtained from {TN + E(R N )}(R N ) = (R N ) which can be reduced to the Schrdinger eauation for the harmonic oscillator