TY - JOUR

T1 - Two-body Schrödinger wave functions in a plane-wave basis via separation of dimensions

AU - Jerke, Jonathan

AU - Poirier, Bill

N1 - Publisher Copyright:
© 2018 Author(s).
Copyright:
Copyright 2018 Elsevier B.V., All rights reserved.

PY - 2018/3/14

Y1 - 2018/3/14

N2 - Using a combination of ideas, the ground and several excited electronic states of the helium atom and the hydrogen molecule are computed to chemical accuracy - i.e., to within 1-2 mhartree or better. The basic strategy is very different from the standard electronic structure approach in that the full two-electron six-dimensional (6D) problem is tackled directly, rather than starting from a single-electron Hartree-Fock approximation. Electron correlation is thus treated exactly, even though computational requirements remain modest. The method also allows for exact wave functions to be computed, as well as energy levels. From the full-dimensional 6D wave functions computed here, radial distribution functions and radial correlation functions are extracted - as well as a 2D probability density function exhibiting antisymmetry for a single Cartesian component. These calculations support a more recent interpretation of Hund's rule, which states that the lower energy of the higher spin-multiplicity states is actually due to reduced screening, rather than reduced electron-electron repulsion. Prospects for larger systems and/or electron dynamics applications appear promising.

AB - Using a combination of ideas, the ground and several excited electronic states of the helium atom and the hydrogen molecule are computed to chemical accuracy - i.e., to within 1-2 mhartree or better. The basic strategy is very different from the standard electronic structure approach in that the full two-electron six-dimensional (6D) problem is tackled directly, rather than starting from a single-electron Hartree-Fock approximation. Electron correlation is thus treated exactly, even though computational requirements remain modest. The method also allows for exact wave functions to be computed, as well as energy levels. From the full-dimensional 6D wave functions computed here, radial distribution functions and radial correlation functions are extracted - as well as a 2D probability density function exhibiting antisymmetry for a single Cartesian component. These calculations support a more recent interpretation of Hund's rule, which states that the lower energy of the higher spin-multiplicity states is actually due to reduced screening, rather than reduced electron-electron repulsion. Prospects for larger systems and/or electron dynamics applications appear promising.

UR - http://www.scopus.com/inward/record.url?scp=85043520696&partnerID=8YFLogxK

U2 - 10.1063/1.5017621

DO - 10.1063/1.5017621

M3 - Article

C2 - 29544282

AN - SCOPUS:85043520696

VL - 148

JO - The Journal of Chemical Physics

JF - The Journal of Chemical Physics

SN - 0021-9606

IS - 10

M1 - 104101

ER -