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實驗九 預測化學反應途徑與反應速率. 49912001 趙珮鈞 49912044 鄭宇娟. 工作分配. 趙珮鈞:目的、原理 鄭宇娟:原理、實驗流程、數據處理. 目的. 1. 以電腦為工具探討化學反應。 2. 解分子之 electronic Schrödinger equation 藉以預測分子結構、反應途徑、過渡態、中間產物、產物。 3. 熟悉分子計算程式: Gaussian 03,Gauss View, 以及分子繪圖程式: Chem Draw 。 4. 計算反應速率常數,並得出產量。. 原理. Born-Oppenheimer approximation - PowerPoint PPT Presentation
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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
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