Electron pair localization function: A practical tool to visualize electron localization in molecules from quantum Monte Carlo data

Anthony Scemama (1) , Patrick Chaquin (2) , Michel Caffarel (1)

1 LCPQ - Laboratoire de Chimie et Physique Quantiques
2 LCT - Laboratoire de chimie théorique

In this work we introduce an electron localization function describing the pairing of electrons in a molecular system. This function, called "electron pair localization function," is constructed to be particularly simple to evaluate within a quantum Monte Carlo framework. Two major advantages of this function are the following: (i) the simplicity and generality of its definition; and (ii) the possibility of calculating it with quantum Monte Carlo at various levels of accuracy (Hartree-Fock, multiconfigurational wave functions, valence bond, density functional theory, variational Monte Carlo with explicitly correlated trial wave functions, fixed-node diffusion Monte Carlo, etc). A number of applications of the electron pair localization function to simple atomic and molecular systems are presented and systematic comparisons with the more standard electron localization function of Becke and Edgecombe are done. Results illustrate that the electron pair localization function is a simple and practical tool for visualizing electronic localization in molecular systems.

Domaines: Chimie théorique et/ou physique

Anthony Scemama, Patrick Chaquin, Michel Caffarel. Electron pair localization function: A practical tool to visualize electron localization in molecules from quantum Monte Carlo data. Journal of Chemical Physics, 2004, 121 (4), pp.1725-1735. ⟨10.1063/1.1765098⟩. ⟨hal-00875621⟩