このエントリーをはてなブックマークに追加 follow us in feedly BACK<< >>NEXT

2. Eight Atomic Integrals Over Hyperbolic Prolate Spheroidal Coordinates For The Lowest State's Energy Of Hydrogen Molecular

Simple Hydrogen Molecular is two electron and two nuclear. The grand state energy of the Hydrogen Molecular is calculated with Slater function 1s electronic orbital. As the approximation, Valence Bond orbital method (VB method or HL method, W. Heitler and F. London) or Simple LCAO Molecular Orbital Method (MO method) are used, and the integrals are calculated with Hamilton-Jacobi method over hyperbolic Confocal Elliptic coordinates (hyperbolic Prolate Spheroidal coordinate).

The Hamiltonian of Hydrogen Molecular electronic orbital is below.
The Hamiltonian of Hydrogen Molecular electronic orbital

12 and ∇22 are the Laplacians of electron 1 and electron 2, respectively. rAB is the distance of nuclear A from nuclear B, and is constant according to Born Oppenheimer approximation in the electronic orbital of Schrödinger equation. The nuclear motions involving the vibration and the rotation is not discussed here.

The wave function involving the spin function must be anti-symmetric under the exchange of electron 1 and electron 2. Therefore the lowest energy level electronic wave function, with the singlet spin function, of VB method and the simplest LCAO MO method are as below, respectively.

The wave function of VB method
The ground energy state's electronic wave function involving the spin function for the VB method of Hydrogen Molecular

The wave function of the simplest LCAO MO method
The ground energy state's electronic wave function involving the spin function for the simplest LCAO MO method of Hydrogen Molecular

S is overlap integral as below.


The lowest energy of VB method and the simplest LCAO MO method are EVB + and EMO + respectively.
EVB + for VB method is expressed as below.


Below spin function integral is 0, because of the spin function orthogonality.


And below spin function integral is 1, because of the spin function normalization.


The lowest energy of VB method
Therefore EVB+ for VB method is expressed as below.
The ground state's energy for the VB method of Hydrogen Molecular

The lowest energy of the simplest LCAO MO method
From the same procedure, EMO+ for the simplest LCAO MO method is expressed as below. The ground state's energy for the simplest LCAO MO method of Hydrogen Molecular

The Hydrogen non-perturbation energy EH and the Normalization equation are as below.


As a result, eight integrals remain in EVB + and EMO +.


Preparation

Before eight integrals calculation, Electronic Orbital, Coordinates Patterns, and MyLibrary are mentioned in this preparation.


○Electronic Orbital


 

 





○Coordinates Patterns

This Page Top









このエントリーをはてなブックマークに追加 follow us in feedly
Home Top BACK<< >>NEXT