PNNL

Abstract

The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. Solvation effects are essential components of all liquid-state chemistry, and it is impossible to understand liquid-phase organic, biological, or inorganic chemistry without including them. The Nobel-Prize-winning gas-phase quantum mechanical electronic structure methods of Pople1 and Kohn et al.2 require the additional inclusion of solvent for reliably addressing problems in liquid-phase chemistry. Methods that include the solvent implicitly are especially powerful because they allow one to retain the minimal representation of the solute, thereby facilitating progress with quantum mechanical calculations at the same high levels as those used in the gas phase,3,4 and because they allow one to model the solvent with the correct bulk permittivity. Reliable calculations of solutes in solution must take account of electrostatics, cavitation, dispersion, and solvent structure, but solvation effects are frequently dominated by electrostatics. Therefore, achieving a solid understanding of electrostatic solvation effects is an excellent starting point for understanding solvation and improving solvation models.