49912001

49912044

1.

2.electronic Schrdinger equation

3.Gaussian 03,Gauss View,Chem Draw

4.

Born-Oppenheimer approximation

Hatree-Fock method

Basis set6-31G

Reaction rate constant (Eyring equation)

A

B

C

AB

AC

Schrdinger equation

Eigenfunction

Eigenvector

Eigenvalue

Born-Oppenheimer approximation

i

j

Time-independent

Born-Oppenheimer approximation

Nuclear

electron

Schrdinger equation Schrdinger equation

electronic Schrdinger equation

U= electronic energy including internuclear repulsion

Schrdinger equation

Hamiltonian

Born-Oppenheimer approximation

Hatree-Fock method

ground state wave function ground state energy

(Slater determinant)

wave function

wave function

(2n)!2n

Coulomb integrals

Exchange integrals

(1)

Hatree- Fock Equation

SCF

HF

Hatree- Fock energy

Kbasis set

Hatree-Fock method

1.

2. HF

3. HF HF

Basis set

(basis functions) (basis set)

Slater-type orbital (STO)

Gaussian-type functions (GTO)

A

B

GTO GTO

Contracted Gaussian-type functions (CGTF)

Cartesian Gaussian 29) exponents(Z)primitive Gaussians

minimal basis set

CGTF

C

1S

2S

2P

STO-3G basis set

double-zeta (DZ) basis set

CGTF

split-valence double-zeta basis set

DZminimal basis setD95V, 3-21G, 6-31G

6-31G

6 primitive Gaussians CGTF

3 primitive Gaussians CGTF

1 exponent uncontracted GTO CGTF

Eyring Equation

: transition state or activated complex

transition state

reactant

A,B

products

potential

energy

Reaction coordinate

( assuming ideal gas : )

if in gas :

(

If the vibration-like motion along reaction coordinate has a frequency

frequency of approaching P is also

: transmission coefficient

to get

Products can be formed if transition state is passed

to get

( where

: standard molar partition function )

Note : we look at vibration mode of along reaction coordinate

for this special mode

( let )

( Eyring equation )

A

B

C

AB

AC

0

THE END

1

2