Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Liquid Water from First Principles: Validation of Different Sampling Approaches

Journal Article · · Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical
OSTI ID:15014181
; ; ; ; ; ; ; ; ; ; ;
A series of first principles molecular dynamics and Monte Carlo simulations were carried out for liquid water to assess the validity and reproducibility of different sampling approaches. These simulations include Car-Parrinello molecular dynamics simulations using the program CPMD with different values of the fictitious electron mass in the microcanonical and canonical ensembles, Born-Oppenheimer molecular dynamics using the programs CPMD and CP2K in the microcanonical ensemble, and Metropolis Monte Carlo using CP2K in the canonical ensemble. With the exception of one simulation for 128 water molecules, all other simulations were carried out for systems consisting of 64 molecules. It is found that the structural and thermodynamic properties of these simulations are in excellent agreement with each other as long as adiabatic sampling is maintained in the Car-Parrinello molecular dynamics simulations either by choosing a sufficiently small fictitious mass in the microcanonical ensemble or by Nos{acute e}-Hoover thermostats in the canonical ensemble. Using the Becke-Lee-Yang-Parr exchange and correlation energy functionals and norm-conserving Troullier-Martins or Goedecker-Teter-Hutter pseudopotentials, simulations at a fixed density of 1.0 g/cm{sup 3} and a temperature close to 315 K yield a height of the first peak in the oxygen-oxygen radial distribution function of about 3.0, a classical constant-volume heat capacity of about 70 J K{sup -1} mol{sup -1}, and a self-diffusion constant of about 0.1 Angstroms{sup 2}/ps.
Research Organization:
Lawrence Livermore National Laboratory (LLNL), Livermore, CA
Sponsoring Organization:
USDOE
DOE Contract Number:
W-7405-ENG-48
OSTI ID:
15014181
Report Number(s):
UCRL-JRNL-204315
Journal Information:
Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical, Journal Name: Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical Journal Issue: 34 Vol. 108; ISSN 1089-5647; ISSN JPCBFK
Country of Publication:
United States
Language:
English

Similar Records

Toward a Monte Carlo program for simulating vapor-liquid phase equilibria from first principles
Journal Article · Wed Oct 20 00:00:00 EDT 2004 · Computer Physics Communication, vol. 169, no. 1-3, April 1, 2005, pp. 8 · OSTI ID:950086
Isobaric-isothermal Monte Carlo simulations from first principles: Application to liquid water at ambient conditions
Journal Article · Wed Dec 01 23:00:00 EST 2004 · ChemPhysChem · OSTI ID:950083
TIME-DEPENDENT PROPERTIES OF LIQUID WATER: A COMPARISON OF CAR-PARRINELLO AND BORN-OPPENHIEMER MOLECULAR DYNAMICS SIMULATIONS
Journal Article · Wed Dec 28 23:00:00 EST 2005 · Journal of Chemical Theory and Computataion, vol. 2, no. 5, September 12, 2006, pp. 1274-1281 · OSTI ID:946249

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ELECTRON CORRELATION
SAMPLING
SPATIAL DISTRIBUTION
SPECIFIC HEAT
THERMODYNAMIC PROPERTIES
VALIDATION
WATER