TransWikia.com

Interpretation of Coulomb operator in Hartree-Fock equation

Physics Asked on April 9, 2021

I have read in a textbook (Modern Quantum Chemistry Szabo and Ostlund) that the Coulomb operator of the form
begin{equation}
mathcal{J}_{j}left(mathbf{x}_{1}right)=int d mathbf{x}_{2}left|chi_{j}left(mathbf{x}_{2}right)right|^{2}r_{12}^{-1}
end{equation}

describes the average local potential at $mathbf{x}_{1}$ arising from the charge distribution from an electron in $chi_{j}$. And therefore the term $sum_{j neq i}left[int d mathbf{x}_{2}left|chi_{j}left(mathbf{x}_{2}right)right|^{2} r_{12}^{-1}right] chi_{i}left(mathbf{x}_{1}right)$ for an $N$-electron system gives the total averaged potential of $N-1$ electrons in other spin orbitals on the electron in $chi_{i}$.

However, if one expands the sum
begin{equation}
sum_{j neq i}left[int d mathbf{x}_{2}left|chi_{j}left(mathbf{x}_{2}right)right|^{2} r_{12}^{-1}right] chi_{i}left(mathbf{x}_{1}right) = left(int d mathbf{x}_{2}left|chi_{1}left(mathbf{x}_{2}right)right|^{2}r_{12}^{-1} + int d mathbf{x}_{2}left|chi_{2}left(mathbf{x}_{2}right)right|^{2}r_{12}^{-1} +…right) chi_{i}left(mathbf{x}_{1}right)
end{equation}

it is indeed a sum over the spin orbital but not of the electrons in the system. My interpretation for the sum is as follows: the total averaged potential acting on electron 1 due to the charge distribution of electron 2 in $N-1$ spin orbitals. I think it has something to do with the fact that electrons are indistinguishable so one cannot assign an electron to an orbital. However, I think the Hartree Fock integro-differential equation
begin{equation}
hleft(mathbf{x}_{1}right) chi_{i}left(mathbf{x}_{1}right)+sum_{j neq i}left[int d mathbf{x}_{2}left|chi_{j}left(mathbf{x}_{2}right)right|^{2} r_{12}^{-1}right] chi_{i}left(mathbf{x}_{1}right)-sum_{j neq i}left[int d mathbf{x}_{2} chi_{j}^{*}left(mathbf{x}_{2}right) chi_{i}left(mathbf{x}_{2}right) r_{12}^{-1}right] chi_{j}left(mathbf{x}_{1}right)=epsilon_{i} chi_{i}left(mathbf{x}_{1}right)
end{equation}

was derived for hydrogen molecule. Is it the same for an $N$-electron system?

One Answer

Short answer: the source of the confusion seems to be that you think the variable $x_2$ refers to the second electron, but that's not true.

My interpretation for the sum is as follows: the total averaged potential acting on electron 1 due to the charge distribution of electron 2 in ?−1 spin orbitals.

No, the variable $x_2$ is just some dummy integration variable. To avoid confusion, it should have been called something like $y$ or $r$.

The logic of the approximation being made is as follows. We are trying to find the wavefunction for some particular orbital $i$. So instead of trying to solve the full multi-electron Schrodinger equation, we will just replace all the other orbitals with a classical distribution of charge.

Answered by ReasonMeThis on April 9, 2021

Add your own answers!

Ask a Question

Get help from others!

© 2024 TransWikia.com. All rights reserved. Sites we Love: PCI Database, UKBizDB, Menu Kuliner, Sharing RPP