Premium
Electronic energy functionals: Levy–Lieb principle within the ground state path integral quantum Monte Carlo
Author(s) -
Delle Site Luigi,
Ghiringhelli Luca M.,
Ceperley David M.
Publication year - 2012
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.24321
Subject(s) - path integral formulation , statistical physics , quantum monte carlo , physics , path integral monte carlo , context (archaeology) , orbital free density functional theory , density functional theory , ground state , monte carlo method , quantum , electron , path (computing) , probability density function , coulomb , quantum mechanics , mathematics , time dependent density functional theory , computer science , paleontology , statistics , biology , programming language
Abstract We propose a theoretical/computational protocol based on the use of the Ground State Path Integral Quantum Monte Carlo for the calculation of the kinetic and Coulomb energy density for a system of N interacting electrons in an external potential. The idea is based on the derivation of the energy densities via the ( N − 1)‐conditional probability density within the framework of the Levy–Lieb constrained search principle. The consequences for the development of energy functionals within the context of density functional theory are discussed. We propose also the possibility of going beyond the energy densities and extend this idea to a computational procedure where the ( N − 1)‐conditional probability is an implicit functional of the electron density, independently from the external potential. In principle, such a procedure paves the way for an on‐the‐fly determination of the energy functional for any system. © 2012 Wiley Periodicals, Inc.