The influence of temperature and density functional models in ab initio molecular dynamics simulation of liquid water.

The performance of density functional theory methods for the modeling of condensed aqueous systems is hard to predict and validation by ab initio molecular simulation of liquid water is absolutely necessary. In order to assess the reliability of these tests, the effect of temperature on the structure and dynamics of liquid water has been characterized with 16 simulations of 20 ps in the temperature range of 280-380 K. We find a pronounced influence of temperature on the pair correlation functions and on the diffusion constant including nonergodic behavior on the time scale of the simulation in the lower temperature range (which includes ambient temperature). These observations were taken into account in a consistent comparison of a series of density functionals (BLYP, PBE, TPSS, OLYP, HCTH120, HCTH407). All simulations were carried out using an ab initio molecular dynamics approach in which wave functions are represented using Gaussians and the density is expanded in an auxiliary basis of plane waves. Whereas the first three functionals show similar behavior, it is found that the latter three functionals yield more diffusive dynamics and less structure.

[1]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[2]  Kenneth T. Gillen,et al.  Self‐Diffusion in Liquid Water to −31°C , 1972 .

[3]  R. A. Santen,et al.  Ab initio molecular dynamics simulation of liquid water and water-vapor interface , 2001 .

[4]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[5]  G. Scuseria,et al.  Climbing the density functional ladder: nonempirical meta-generalized gradient approximation designed for molecules and solids. , 2003, Physical review letters.

[6]  A. Becke,et al.  Density-functional exchange-energy approximation with correct asymptotic behavior. , 1988, Physical review. A, General physics.

[7]  Matthias Krack,et al.  Water structure as a function of temperature from X-ray scattering experiments and ab initio molecular dynamics , 2003 .

[8]  S. Goedecker,et al.  Relativistic separable dual-space Gaussian pseudopotentials from H to Rn , 1998, cond-mat/9803286.

[9]  Bin Chen,et al.  Liquid Water from First Principles: Investigation of Different Sampling Approaches , 2004 .

[10]  Alan K. Soper,et al.  The radial distribution functions of water and ice from 220 to 673 K and at pressures up to 400 MPa , 2000 .

[11]  Teter,et al.  Separable dual-space Gaussian pseudopotentials. , 1996, Physical review. B, Condensed matter.

[12]  Michele Parrinello,et al.  Structural, electronic, and bonding properties of liquid water from first principles , 1999 .

[13]  Kari Laasonen,et al.  ‘‘Ab initio’’ liquid water , 1993 .

[14]  Michiel Sprik,et al.  Ab initio molecular dynamics simulation of liquid water: Comparison of three gradient‐corrected density functionals , 1996 .

[15]  M. Klein,et al.  Hydrogen bonding in water. , 2003, Physical review letters.

[16]  G. Voth,et al.  Car–Parrinello molecular dynamics simulation of liquid water: New results , 2002 .

[17]  Fred A. Hamprecht,et al.  Development and assessment of new exchange-correlation functionals , 1998 .

[18]  Greg L. Hura,et al.  A high-quality x-ray scattering experiment on liquid water at ambient conditions , 2000 .

[19]  Michele Parrinello,et al.  A hybrid Gaussian and plane wave density functional scheme , 1997 .

[20]  Nicholas C. Handy,et al.  A dynamical correlation functional , 2002 .

[21]  Michiel Sprik,et al.  New generalized gradient approximation functionals , 2000 .

[22]  J. VandeVondele,et al.  An efficient orbital transformation method for electronic structure calculations , 2003 .

[23]  Free energy of liquid water on the basis of quasichemical theory and ab initio molecular dynamics. , 2003, Physical review. E, Statistical, nonlinear, and soft matter physics.

[24]  A. Daniel Boese,et al.  A new parametrization of exchange–correlation generalized gradient approximation functionals , 2001 .

[25]  J. Bertrán,et al.  Effect of Counterpoise Correction on the Geometries and Vibrational Frequencies of Hydrogen Bonded Systems , 2001 .