Electronic confinement effects on the reaction field type calculations of solvent effects

摘要

We analyze some procedures to introduce the effect of confining the electrons of the hydrogen atoms in cavitation spheres like those used in the self-consistent reaction field models for studying the solvent influence on molecular properties [as polarizable continuum model (PCM), or conductor screening model (COSMO)]. We have found that the boundary conditions to be applied have an important effect on the system energy that by no means should be neglected in this type of calculations. We have found as well that "-nG" expansion technique could be applicable in this kind of calculations (even at the very simple "-3G" level) and lead us to a relatively simple form of applying the theory. Moreover, we have found a way to define the cavitation radius of PCM calculations, by minimizing the system energy with respect to this parameter, which could be a more satisfactory procedure - at least from a theoretical point of view - than the use of empirical values characteristic of most of the PCM or COSMO standard calculations.