A 'first principles' potential energy surface for liquid water from VRT spectroscopy of water clusters.
We present results of gas phase cluster and liquid water simulations from the recently determined VRT(ASP-W)III water dimer potential energy surface (the third fitting of the Anisotropic Site Potential with Woermer dispersion to vibration-rotation-tunnelling data). VRT(ASP-W)III is shown to not only be a model of high 'spectroscopic' accuracy for the water dimer, but also makes accurate predictions of vibrational ground-state properties for clusters up through the hexamer. Results of ambient liquid water simulations from VRT(ASP-W)III are compared with those from ab initio molecular dynamics, other potentials of 'spectroscopic' accuracy and with experiment. The results herein represent the first time to the authors' knowledge that a 'spectroscopic' potential surface is able to correctly model condensed phase properties of water.
Goldman
Nir
N
Lawrence Livermore National Laboratory, Chemistry and Materials Science Directorate, L-268, Livermore, CA 94551, USA.
Leforestier
Claude
C
Saykally
R J
RJ
D003198:Computer Simulation; D003461:Crystallography / Q000379:methods; D004735:Energy Transfer; D046911:Macromolecular Substances / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D044367:Phase Transition; D012996:Solutions / Q000737:chemistry; D013057:Spectrum Analysis / Q000379:methods*; D013500:Surface Tension; D013696:Temperature; D014867:Water / Q000737:chemistry*
D046911:Macromolecular Substances; D012996:Solutions; D014867:Water