A study of molecular vibrational relaxation mechanism in condensed phase based upon mixed quantum-classical molecular dynamics.Noncollisional mechanism for the relaxation of a polar solute supercritical water

摘要

Mixed quantum-classical molecular dynamics method has been applied to vibrational relaxation of a hydrophilic model NO in supercritical water at various densities along an isotherm above the critical temperature.The relaxation rate was determined based on Fermi's golden rule at each state point and showed an inverse S-shaped curve as a function of bulk density.The hydration number was also calculated as a function of bulk density based on the calculated radial distribution function,which showed a good correlation with the relaxation rate.Change of the survival probability of the solute vibrational state was analyzed as a function of time together with the trajectory of the solvent water and the interaction with it.We will show that the solvent molecule resides near the solute molecule for a while and the solvent contributes to the relaxation by the random-noiselike Coulombic interaction only when it stays near the solute.After the solvent leaves the solute,it shows no contribution to the relaxation.The relaxation mechanism for this system is significantly different from the collisional one found for a nonpolar solute in nonpolar solvent in Paper I.Then,the relaxation rate is determined,on average,by the hydration number or local density of the solvent.Thus,the density dependence of the relaxation rate for the polar solute in supercritical water is apparently similar to that found for the nonpolar solute in nonpolar solvent,although the molecular process is quite different from each other.