Coupling quantum Monte Carlo to a nonlinear polarizable continuum model for spherical solutes.
Starting from the nonlinear dielectric response model of Sandberg and Edholm, we derive an analytical expression of the polarization contribution to the solvation free energy in terms of the electronic density of the solute and the dielectric properties of the solvent. The solvent inhomogeneity is taken into account with the use of a smooth switching function whose spacial variation is established on the basis of how the solvent is arranged around the solute. An explicit form of a local potential representing the solvent effect on the solute is thus obtained by functional analysis. This effective potential can be combined with density functional or quantum chemical methods for the quantum mechanical treatment of the solute. Here, we use quantum Monte Carlo techniques for the solute and apply the method to the hydration of atomic ions finding very good agreement with experimental data.
Amovilli
Claudio
C
Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via Risorgimento 35, I-56126 Pisa, Italy. amovilli@dcci.unipi.it
Filippi
Claudia
C
Floris
Franca Maria
FM