title: Self-Consistent Field and Polarizable Continuum Model: A New Strategy of Solution for the Coupled Equations.
abstract: We present a new strategy for the solution of the self-consistent field (SCF) equations when solvent effects are included by means of the polarizable continuum model (PCM). By exploiting the recently introduced variational formalism of the PCM (VPCM), we are able to recast the self-consistent reaction field problem as an energy functional of both electronic and polarization degrees of freedom. The variational minimization of such a functional leads to the free energy of the solvated molecule at a given geometry. In this contribution we describe an effective procedure and its implementation to achieve the solution of such a variational problem. Moreover, we present numerical evidence that the new approach is superior to the traditional one in terms of performance, especially when a relatively inexpensive semiempirical method is used to describe medium- and large-size solutes.
authors.affiliation: Scuola Normale Superiore , Piazza dei Cavalieri 7, 56126 Pisa, Italy.
authors.forename: Filippo
authors.initials: F
authors.lastname: Lipparini
authors.affiliation: Gaussian, Inc. , 340 Quinnipiac Street Building 40, Wallingford, Connecticut 06492, United States.
authors.forename: Giovanni
authors.initials: G
authors.lastname: Scalmani
authors.affiliation: Dipartimento di Chimica e Chimica Industriale, Università di Pisa , Via Risorgimento 35, 56126 Pisa, Italy.
authors.forename: Benedetta
authors.initials: B
authors.lastname: Mennucci
authors.affiliation: Gaussian, Inc. , 340 Quinnipiac Street Building 40, Wallingford, Connecticut 06492, United States.
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Frisch