Study of solvent effects by means of averaged solvent electrostatic potentials obtained from molecular dynamics data

✍ Scribed by Sanchez, M. L.; Aguilar, M. A.; del Valle, F. J. Olivares

• Publisher: John Wiley and Sons
• Year: 1997
• Tongue: English
• Weight: 282 KB
• Volume: 18
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/(sici)1096-987x(199702)18:3<313::aid-jcc2>3.0.co;2-x

✦ Synopsis

We present the theory and implementation of a new approach for studying solvent effects. The electronic structure of the solute, calculated at the ab initio level, is obtained in the presence of the surrounding medium. We employ a mean field theory in which the solvent response is described by means of point charges chosen in such a way that they reproduce the average value of the solvent electrostatic potential calculated from molecular dynamics data. In this way, the complete solvent potential can be introduced into the solute Hamiltonian without making use of a one-center multiple expansion of the solute᎐solvent potential. In the proposed method, only one quantum calculation has to be performed and a great number of configurations can easily be included making the calculation statistically significant. We show that, despite the large fluctuations in the solute charge distribution induced by the solvent, the proposed mean field theory adequately reproduces the energetics and properties of formamide and water molecules in aqueous solution.