Two exchange-correlation functionals compared for first-principles liquid water.pdf

a r X i v : c o n d - m a t / 0 4 0 7 7 2 4 v 2 [ c o n d - m a t .s o f t ] 1 3 J u l 2 0 0 5 Two exchange-correlation functionals compared for first-principles liquid water M. V. Ferna?ndez-Serra,1, ? G. Ferlat,2 and Emilio Artacho1 1Department of Earth Sciences, University of Cambridge, Downing street, Cambridge CB2 3EQ, UK 2Laboratoire de Mine?ralogie-Cristallographie, Universite? Pierre et Marie Curie, Paris, France (Dated: 27 July 2004) The first-principles description of liquid water using ab initio molecular dynamics (AIMD) based on Density Functional theory (DFT) has recently been found to require long equili- bration times, giving too low diffusivities and a clear over-structuring of the liquid. In the light of these findings we compare here the room-temperature description offered by two dif- ferent exchange correlation functionals: BLYP, the most popular for liquid water so far, and RPBE, a revision of the widely used PBE. We find for RPBE a less structured liquid with radial distribution functions closer to the experimental ones than the ones of BLYP. The diffusivity obtained with RPBE for heavy water is still 20% lower than the corresponding experimental value, but it represents a substantial improvement on the BLYP value, one order of magnitude lower than experiment. These characteristics and the hydrogen-bond (HB) network imperfection point to an effective temperature ～3% lower than the actual simulation temperature for the RPBE liquid, as compared with BLYP’s ～17% deviation. The too long O–O average nearest-neighbor distance observed points to an excessively weak HB, possibly compensating more fundamental errors in the DFT description. I. INTRODUCTION The interaction of organic pollutant molecules with the minerals and other components of the soil represents a paradigmatic case within the set of atomic-scale problems of relevance for the environment. It displays the level of complexity that demands a fundamental revision of the way we use co