Prediction of many-electron wavefunctions using atomic potentials

Abstract

For a given many-electron molecule, it is possible to define a corresponding one-electron Schrödinger 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.

arXiv comment14 pages

References in corpus (2)

• A Classical Background for the Wave Function Prediction in the Infinite System DMRG Method
• Electron correlation by polarization of interacting densities

Cited by in corpus (5)

• An assessment of initial guesses for self-consistent field calculations. Superposition of Atomic Potentials: simple yet efficient
• Efficient implementation of the superposition of atomic potentials initial guess for electronic structure calculations in Gaussian basis sets
• Atomic effective potentials for starting molecular electronic structure calculations
• Prediction of many-electron wavefunctions using atomic potentials: extended basis sets and molecular dissociation
• Prediction of many-electron wavefunctions using atomic potentials: refinements and extensions to transition metals and large systems