Comparison of the structure of harmonic aqueous glasses and liquid water.
Glassy structures of water were generated by rapidly quenching configurations of 64 and 343 molecules of liquid water. The potential energy was then expanded through quadratic order around local minima generated this way and properties of the resulting harmonic system were calculated. The results were used to test the extent to which the structure of liquid water is similar to that of a harmonic aqueous glass. The radial distribution functions for the glass are remarkably similar to those of the liquid. The vibrational density of states for the glassy water exhibits a gap between 300 and 400 cm-1. The normal modes below 300 cm-1 correspond to molecular translations while the modes above 400 cm-1 are ascribed to molecular librations. Translational modes are almost entirely responsible for the broadening of oxygen-oxygen radial distribution function of the quenched configuration. They are also primarily responsible for the broadening of other radial distribution functions.  Vibrational density of states leads to classical and quantum free energies for the harmonic system equal -9.62 +/- 0.12 and -8.89 +/- 0.12 kcal/mol, respectively, at T = 300 K. Both free energies were found to be insensitive to sample size and to the configurational differences between the quenched structures.
Pohorille
A
A
Department of Chemistry, University of California, Berkeley 94720, USA.
Pratt
L R
LR
LaViolette
R A
RA
Wilson
M A
MA
MacElroy
R D
RD
D003198:Computer Simulation; D005898:Glass; D006859:Hydrogen; D007053:Ice; D008962:Models, Theoretical; D015394:Molecular Structure; D010100:Oxygen; D013816:Thermodynamics; D014867:Water / Q000737:chemistry*
D007053:Ice; D014867:Water; D006859:Hydrogen; D010100:Oxygen