Abstract
Solvation in supercritical water under equilibrium and nonequilibrium conditions is studied via molecular dynamics simulations. The influence of solute charge distributions and solvent density on the solvation structures and dynamics is examined with a diatomic probe solute molecule. It is found that the solvation structure varies dramatically with the solute dipole moment, especially in low-density water, in accord with many previous studies on ion solvation. This electrostrictive effect has important consequences for solvation dynamics. In the case of a nonequilibrium solvent relaxation, if there are sufficiently many water molecules close to the solute at the outset of the relaxation, the solvent response measured as a dynamic Stokes shift is almost completely governed by inertial rotations of these water molecules. By contrast, in the opposite case of a low local solvent density near the solute, not only rotations but also translations of water molecules play an important role in solvent relaxation dynamics. The applicability of a linear response is found to be significantly restricted at low water densities.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
