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Inequivalent electron densities derived from an approximate correlated ground‐state wave function using the Hiller–Sucher–Feinberg identity: Comparisons with quantum Monte Carlo densities for He and Ne atoms
Author(s) -
Amovilli Claudio,
March Norman H.
Publication year - 2008
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.21920
Subject(s) - quantum monte carlo , wave function , diffusion monte carlo , density matrix , electron density , ground state , neon , electron , physics , atom (system on chip) , quantum , fock space , monte carlo method , chemistry , quantum mechanics , atomic physics , monte carlo molecular modeling , markov chain monte carlo , argon , mathematics , statistics , computer science , embedded system
The Hiller–Sucher–Feinberg (HSF) identity is combined with the three‐parameter correlated wave function of Chandrasekhar in order to generate an alternative electron density ρ( r ) for the He atom. This and the conventional “local” operator form of ρ( r ) are then compared with a diffusion quantum Monte Carlo density. An exact limiting relation is also presented, via HSF identity, between the one‐particle density matrix and the pair density in a many‐electron atom, which transcends its Hartree–Fock counterpart and has no N ‐representability difficulties. For the Ne atom, the accuracy of the semiempirical correlated electron density recently obtained by Cordero et al. (Phys. Rev. A 2007, 75, 052502) using fine‐tuning of Hartree–Fock theory was assessed by appealing to the ground‐state density from diffusion quantum Monte Carlo. The high accuracy of the Cordero et al. density was thereby confirmed. A HSF calculation on neon, with a correlated many‐body wave function as starting point, is a worthwhile future aim. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009