First-principles molecular dynamics simulations, in which the forces are computed from electronic structure calculations, have great potential to provide unique insight into structure, dynamics, electronic properties, and chemistry of interfacial systems that is not available from empirical force fields. The majority of current first-principles simulations are driven by forces derived from density functional theory with generalized gradient approximations to the exchange-correlation energy, which do not capture dispersion interactions. We have carried out first-principles molecular dynamics simulations of air-water interfaces employing a particular generalized gradient approximation to the exchange-correlation functional (BLYP), with and without empirical dispersion corrections. We assess the utility of the dispersion corrections by comparison of a variety of structural, dynamic, and thermodynamic properties of bulk and interfacial water with experimental data, as well as other first-principles and force field-based simulations.
|Original language||English (US)|
|Journal||Journal of Chemical Physics|
|State||Published - Sep 28 2011|
Bibliographical noteFunding Information:
This work was performed under the auspices of the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences, (U.S.) Department of Energy (DOE), under Contract No. DE-AC06-76RLO 1830 with Battelle Memorial Institute, which operates the Pacific Northwest National Laboratory (PNNL), a multiprogram national laboratory. This research was performed in part using the computational resources in the National Energy Research Supercomputing Center (NERSC) at Lawrence Berkeley National Laboratory, the Molecular Sciences Computing Facility at PNNL (via an EMSL Pilot Project award to D.J.T. and C.J.M.). Additional support from the National Science Foundation (NSF) (CBET-0756641 to J.I.S., OISE-0853294 to M.J.M., and CHE-0431512 to D.J.T.) is gratefully acknowledged. Part of this work performed under the auspices of the (U.S.) DOE by Lawrence Livermore National Laboratory under Contract No. DE-AC52-07NA27344 with computing support from M&IC Program and Institutional Grand Challenge Award. M.D.B. is grateful for support from the Linus Pauling Distinguished Postdoctoral Fellowship Program at PNNL.