Electron correlation in Li+, He, H− and the critical nuclear charge system ZC: energies, densities and Coulomb holes. Issue 1 (9th January 2019)

• Record Type: Journal Article
• Authors: Baskerville, Adam L.; King, Andrew W.; Cox, Hazel
• Is Part Of: Royal Society open science. Volume 6:Issue 1(2019)
• Publication Date: 2019-01-09
• Subjects: electron correlation -- Coulomb hole -- intracule density -- two-electron systems -- critical nuclear charge for binding; Science -- Periodicals; 500
• DOI: 10.1098/rsos.181357
• Languages: English
• ISSNs: 2054-5703

Abstract

Abstract : This paper presents high-accuracy correlation energies, intracule densities and Coulomb hole(s) for the lithium cation, helium, hydride ion and the system with the critical nuclear charge, Z C, for binding two electrons. The fully correlated (FC) wave function and the Hartree–Fock (HF) wave function are both determined using a Laguerre-based wave function. It is found that for the lithium cation and the helium atom a secondary Coulomb hole is present, in agreement with a previous literature finding, confirming a counterintuitive conclusion that electron correlation can act to bring distant electrons closer together. However, no evidence for a tertiary Coulomb hole is found. For the hydride anion and the system just prior to electron detachment only a single Coulomb hole is present and electron correlation decreases the probability of finding the electrons closer together at all radial distances. The emergence of a secondary Coulomb hole is investigated and found to occur between Z = 1.15 and Z = 1.20. The FC and HF energies and intracule densities (in atomic units) used to calculate the correlation energy and Coulomb hole, respectively, are accurate to at least the nano-scale for helium and the cation and at least the micro-scale for the anions.