Structure of liquid water at ambient temperature from ab initio molecular dynamics performed in the complete basis set limit.

Structural properties of liquid water at ambient temperature were studied using Car-Parrinello [Phys. Rev. Lett. 55, 2471 (1985)] ab initio molecular dynamics (CPAIMD) simulations combined with the Kohn-Sham (KS) density functional theory and the BLYP exchange-correlation functional for the electronic structure. Unlike other recent work on the same subject, where plane-wave (PW) or hybrid Gaussian/plane-wave basis sets were employed, in the present paper, a discrete variable representation (DVR) basis set is used to expand the KS orbitals, so that with the real-space grid adapted in the present work, the properties of liquid water could be obtained very near the complete basis set limit. Structural properties of liquid water were extracted from a 30 ps CPAIMD-BLYP/DVR trajectory at 300 K. The radial distribution functions (RDFs), spatial distribution functions, and hydrogen bond geometry obtained from the CPAIMD-BLYP/DVR simulation are generally in good agreement with the most up to date experimental measurements. Compared to recent ab initio MD simulations based on PW basis sets, less significant overstructuring was found in the RDFs and the distributions of hydrogen bond angles, suggesting that previous plane-wave and Gaussian basis set calculations have exaggerated the tendency toward overstructuring.

[1]  W. Kohn,et al.  Self-Consistent Equations Including Exchange and Correlation Effects , 1965 .

[2]  A. Ben-Naim.  Statistical Mechanics of “Waterlike” Particles in Two Dimensions. I. Physical Model and Application of the Percus–Yevick Equation , 1971 .

[3]  Car,et al.  Unified approach for molecular dynamics and density-functional theory. , 1985, Physical review letters.

[4]  J. Light,et al.  Generalized discrete variable approximation in quantum mechanics , 1985 .

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

[6]  G. Watson,et al.  Computer simulation , 1988 .

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

[8]  Hamann.  Generalized norm-conserving pseudopotentials. , 1989, Physical review. B, Condensed matter.

[9]  R. Parr.  Density-functional theory of atoms and molecules , 1989 .

[10]  Martins,et al.  Efficient pseudopotentials for plane-wave calculations. , 1991, Physical review. B, Condensed matter.

[11]  Wang,et al.  Correlation hole of the spin-polarized electron gas, with exact small-wave-vector and high-density scaling. , 1991, Physical review. B, Condensed matter.

[12]  Lee,et al.  Ab initio molecular dynamics for d-electron systems: Liquid copper at 1500 K. , 1992, Physical review letters.

[13]  M. Klein,et al.  Nosé-Hoover chains : the canonical ensemble via continuous dynamics , 1992 .

[14]  Lee,et al.  Car-Parrinello molecular dynamics with Vanderbilt ultrasoft pseudopotentials. , 1993, Physical review. B, Condensed matter.

[15]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[16]  Alfredo Pasquarello,et al.  First-principles Molecular Dynamics , 1993 .

[17]  B. Berne,et al.  Efficient molecular dynamics and hybrid Monte Carlo algorithms for path integrals , 1993 .

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

[19]  Michael P. Allen,et al.  Computer simulation in chemical physics , 1993 .

[20]  Michele Parrinello,et al.  Integrating the Car–Parrinello equations. I. Basic integration techniques , 1994 .

[21]  Peter G. Kusalik,et al.  The Spatial Structure in Liquid Water , 1994, Science.

[22]  A. Soper.  Orientational correlation function for molecular liquids: The case of liquid water , 1994 .

[23]  Sotiris S. Xantheas,et al.  Ab initio studies of cyclic water clusters (H2O)n, n=1–6. II. Analysis of many‐body interactions , 1994 .

[24]  Blöchl,et al.  Projector augmented-wave method. , 1994, Physical review. B, Condensed matter.

[25]  M. Klein,et al.  Ab initio molecular dynamics study of hydrochloric acid in water , 1994 .

[26]  Kari Laasonen,et al.  Ab initio molecular dynamics simulation of the solvation and transport of hydronium and hydroxyl ions in water , 1995 .

[27]  Kari Laasonen,et al.  Ab initio molecular dynamics simulation of the solvation and transport of H3O+ and OH- ions in water , 1995 .

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

[29]  Wu,et al.  Molecular dynamics with quantum forces: Vibrational spectra of localized systems. , 1996, Physical review. B, Condensed matter.

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

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

[32]  Sullivan,et al.  Real-space multigrid-based approach to large-scale electronic structure calculations. , 1996, Physical review. B, Condensed matter.

[33]  Ab initio molecular dynamics study of dilute hydrofluoric acid , 1996 .

[34]  Hernández,et al.  Linear-scaling density-functional-theory technique: The density-matrix approach. , 1996, Physical review. B, Condensed matter.

[35]  Michele Parrinello,et al.  From silicon to RNA: The coming of age of ab initio molecular dynamics , 1997 .

[36]  M. Klein,et al.  Ab initio study of aqueous hydrochloric acid , 1997 .

[37]  Alan K. Soper,et al.  Site–site pair correlation functions of water from 25 to 400 °C: Revised analysis of new and old diffraction data , 1997 .

[38]  M. Sprik,et al.  Ab initio molecular dynamics study of the reaction of water with formaldehyde in sulfuric acid solution. , 1998 .

[39]  Ken A. Dill,et al.  A Simple Model of Water and the Hydrophobic Effect , 1998 .

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

[41]  Mark E. Tuckerman,et al.  Quantum dynamics via adiabatic ab initio centroid molecular dynamics , 1999 .

[42]  S. Goedecker.  Linear scaling electronic structure methods , 1999 .

[43]  M. Parrinello,et al.  The nature of the hydrated excess proton in water , 1999, Nature.

[44]  Thomas M Truskett,et al.  A single-bond approach to orientation-dependent interactions and its implications for liquid water , 1999 .

[45]  J. Eland,et al.  The fragmentation dynamics of CS22 , 1999 .

[46]  Sotiris S. Xantheas,et al.  Cooperativity and Hydrogen Bonding Network in Water Clusters , 2000 .

[47]  Johannes Grotendorst,et al.  Modern methods and algorithms of quantum chemistry , 2000 .

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

[49]  Michael W. Mahoney,et al.  A five-site model for liquid water and the reproduction of the density anomaly by rigid, nonpolarizable potential functions , 2000 .

[50]  K. Dill,et al.  A two-dimensional model of water: Theory and computer simulations , 2000 .

[51]  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 .

[52]  Mark E. Tuckerman,et al.  Exploiting multiple levels of parallelism in Molecular Dynamics based calculations via modern techniques and software paradigms on distributed memory computers , 2000 .

[53]  J. Ilja Siepmann,et al.  Development of Polarizable Water Force Fields for Phase Equilibrium Calculations , 2000 .

[54]  A. Luzar.  Resolving the hydrogen bond dynamics conundrum , 2000 .

[55]  T. Beck.  Real-space mesh techniques in density-functional theory , 2000, cond-mat/0006239.

[56]  B. Berne,et al.  Quantum effects in liquid water: Path-integral simulations of a flexible and polarizable ab initio model , 2001 .

[57]  M. Tuckerman,et al.  Ab Initio Molecular Dynamics Investigation of the Concentration Dependence of Charged Defect Transport in Basic Solutions via Calculation of the Infrared Spectrum , 2002 .

[58]  Bin Chen,et al.  Solvation structure and mobility mechanism of OH-: A car-parrinello molecular dynamics investigation of alkaline solutions , 2002 .

[59]  M. Klein,et al.  Structural and Spectral Properties of Aqueous Hydrogen Fluoride Studied Using ab Initio Molecular Dynamics , 2002 .

[60]  M. Parrinello,et al.  The nature and transport mechanism of hydrated hydroxide ions in aqueous solution , 2002, Nature.

[61]  M. Tuckerman.  Ab initio molecular dynamics: basic concepts, current trends and novel applications , 2002 .

[62]  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.

[63]  Bernd G. Pfrommer,et al.  Temperature-dependent hydrogen-bond geometry in liquid water. , 2003, Physical review letters.

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

[65]  Dawn A. Yarne,et al.  Ab initio molecular dynamics calculations with simple, localized, orthonormal real-space basis sets , 2003 .

[66]  J. Kress,et al.  Hydration and mobility of HO-(aq). , 2002, Proceedings of the National Academy of Sciences of the United States of America.

[67]  Edoardo Aprà,et al.  High-level ab initio calculations for the four low-lying families of minima of (H2O)20. I. Estimates of MP2/CBS binding energies and comparison with empirical potentials. , 2004, The Journal of chemical physics.

[68]  Richard J. Saykally,et al.  Energetics of Hydrogen Bond Network Rearrangements in Liquid Water , 2004, Science.

[69]  Giulia Galli,et al.  A first principles simulation of rigid water. , 2004, The Journal of chemical physics.

[70]  Network equilibration and first-principles liquid water. , 2004, The Journal of chemical physics.

[71]  E. Artacho,et al.  Two exchange-correlation functionals compared for first-principles liquid water , 2004, cond-mat/0407724.

[72]  Zhenyu Zhang,et al.  "Lagrange functions": a family of powerful basis sets for real-space order-N electronic structure calculations. , 2004, Physical review letters.

[73]  Roberto Car,et al.  Calculation of near-edge x-ray-absorption fine structure at finite temperatures: spectral signatures of hydrogen bond breaking in liquid water. , 2004, The Journal of chemical physics.

[74]  P. Wernet,et al.  The Structure of the First Coordination Shell in Liquid Water , 2004, Science.

[75]  Francois Gygi,et al.  Towards an assessment of the accuracy of density functional theory for first principles simulations of water. II. , 2004, The Journal of chemical physics.

[76]  I-Feng W. Kuo,et al.  An ab Initio Molecular Dynamics Study of the Aqueous Liquid-Vapor Interface , 2004, Science.

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

[78]  J. Loparo,et al.  Hydrogen bonds in liquid water are broken only fleetingly. , 2005, Proceedings of the National Academy of Sciences of the United States of America.

[79]  Nicola Marzari,et al.  Static and dynamical properties of heavy water at ambient conditions from first-principles molecular dynamics. , 2005, The Journal of chemical physics.

[80]  Joost VandeVondele,et al.  The influence of temperature and density functional models in ab initio molecular dynamics simulation of liquid water. , 2005, The Journal of chemical physics.

[81]  G. Martyna,et al.  Temperature-dependent water structure: Ab initio and empirical model predictions , 2005 .

[82]  Phillip L Geissler,et al.  Unified description of temperature-dependent hydrogen-bond rearrangements in liquid water. , 2005, Proceedings of the National Academy of Sciences of the United States of America.

[83]  P. Wernet,et al.  Comment on "Energetics of Hydrogen Bond Network Rearrangements in Liquid Water" , 2005, Science.

[84]  Gregory A Voth,et al.  Ab initio molecular-dynamics simulation of aqueous proton solvation and transport revisited. , 2005, The Journal of chemical physics.

[85]  A. K. Soper.  An asymmetric model for water structure , 2005 .

[86]  R. Saykally,et al.  Response to Comment on "Energetics of Hydrogen Bond Network Rearrangements in Liquid Water" , 2005, Science.

[87]  The electronic structure of liquid water within density-functional theory. , 2005, The Journal of chemical physics.

[88]  R. Car,et al.  Intermolecular dynamical charge fluctuations in water: a signature of the H-bond network. , 2005, Physical review letters.

[89]  Emilio Artacho,et al.  Electrons and hydrogen-bond connectivity in liquid water. , 2005, Physical review letters.

[90]  Sotiris S Xantheas,et al.  The flexible, polarizable, thole-type interaction potential for water (TTM2-F) revisited. , 2006, The journal of physical chemistry. A.

[91]  Alexander D. MacKerell,et al.  A polarizable model of water for molecular dynamics simulations of biomolecules , 2006 .

[92]  Deprotonation of solvated formic acid: Car-Parrinello and metadynamics simulations. , 2006, The journal of physical chemistry. B.

[93]  M. Tuckerman,et al.  Ab initio molecular dynamics with discrete variable representation basis sets: techniques and application to liquid water. , 2006, The journal of physical chemistry. A.

[94]  Teodora Todorova,et al.  Molecular dynamics simulation of liquid water: hybrid density functionals. , 2006, The journal of physical chemistry. B.

[95]  Margaret E. Johnson,et al.  Tetrahedral structure or chains for liquid water. , 2006, Proceedings of the National Academy of Sciences of the United States of America.

[96]  M. Tuckerman,et al.  The molecular origin of the "continuous" infrared absorption in aqueous solutions of acids: a computational approach. , 2006, Angewandte Chemie.

[97]  M. Tuckerman,et al.  Structure and dynamics of OH-(aq). , 2006, Accounts of chemical research.

[98]  Bin Chen,et al.  Structural correlations and motifs in liquid water at selected temperatures: ab initio and empirical model predictions. , 2006, The journal of physical chemistry. B.

[99]  D. Truhlar,et al.  Assessment of the pairwise additive approximation and evaluation of many-body terms for water clusters. , 2006, The journal of physical chemistry. B.

[100]  Bin Chen,et al.  Relative pKa values from first-principles molecular dynamics: the case of histidine deprotonation. , 2006, The journal of physical chemistry. B.

[101]  Fawzi Mohamed,et al.  Simulating fluid-phase equilibria of water from first principles. , 2006, The journal of physical chemistry. A.

[102]  M. Odelius,et al.  X-Ray Absorption Spectrum of Liquid Water From Molecular Dynamics Simulations: Asymmetric Model , 2006 .

[103]  T. Carrington,et al.  Discrete‐Variable Representations and their Utilization , 2007 .