Prediction of many-electron wavefunctions using atomic potentials

TL;DR

This paper introduces a method to predict many-electron wavefunctions using atomic potentials derived from simple atomic densities, enabling accurate molecular orbital predictions with minimal computational effort.

Contribution

It presents a novel approach to approximate many-electron wavefunctions via atomic potentials, reducing computational complexity while maintaining high accuracy.

Findings

Wavefunctions predicted with less than 0.08 eV deviation from exact energies.

Average atomic potentials are effective across different molecules.

Method provides accurate molecular orbitals without full self-consistent calculations.

Abstract

For a given many-electron molecule, it is possible to define a corresponding one-electron Schr\"odinger equation, using potentials derived from simple atomic densities, whose solution predicts fairly accurate molecular orbitals for single- and multi-determinant wavefunctions for the molecule. The energy is not predicted and must be evaluated by calculating Coulomb and exchange interactions over the predicted orbitals. Potentials are found by minimizing the energy of predicted wavefunctions. There exist slightly less accurate average potentials for first-row atoms that can be used without modification in different molecules. For a test set of molecules representing different bonding environments, these average potentials give wavefunctions with energies that deviate from exact self-consistent field or configuration interaction energies by less than 0.08 eV and 0.03 eV per bond or valence electron pair, respectively.