title: Stereo-electronic, vibrational, and environmental contributions to polarizabilities of large molecular systems: a feasible anharmonic protocol.
abstract: Reliable computations of linear and non-linear optical properties of molecular systems in condensed phases require a proper account of stereo-electronic, vibrational, and environmental effects. In the framework of density functional theory, these effects can be accurately introduced using second-order vibrational perturbation theory in conjunction with polarizable continuum models. We illustrate the combination of an anharmonic description of the ground-state potential energy surface with solvation effects treated with the polarizable continuum model (PCM) in the calculation of the electronic, zero-point, and pure vibrational polarizabilities of selected systems. The description of the solvation environment is enriched by taking into account the dynamical aspects of the solute-solvent interactions through the inclusion of both electronic and vibrational non-equilbrium effects, as well as the direct effect of the solvent on the electric field that generates the molecular response (local field effect). This treatment yields accurate results which can be directly compared with experimental findings without the need of empirical corrections.
authors.affiliation: Scuola Normale Superiore, Piazza dei Cavalieri 7, 56126 Pisa, Italy.
authors.forename: Franco
authors.initials: F
authors.lastname: Egidi
authors.affiliation: Scuola Normale Superiore, Piazza dei Cavalieri 7, 56126 Pisa, Italy.
authors.forename: Tommaso
authors.initials: T
authors.lastname: Giovannini
authors.affiliation: Scuola Normale Superiore, Piazza dei Cavalieri 7, 56126 Pisa, Italy.
authors.forename: Matteo
authors.initials: M
authors.lastname: Piccardo
authors.affiliation: Scuola Normale Superiore, Piazza dei Cavalieri 7, 56126 Pisa, Italy ; Consiglio Nazionale delle Ricerche, Istituto di Chimica dei Composti Organometallici, UOS di Pisa, Via G. Moruzzi 1, 56124 Pisa, Italy.
authors.forename: Julien
authors.initials: J
authors.lastname: Bloino
authors.affiliation: Dipartimento di Chimica e Chimica Industriale, Università di Pisa, via Risorgimento 35, 56126 Pisa, Italy.
authors.forename: Chiara
authors.initials: C
authors.lastname: Cappelli
authors.affiliation: Scuola Normale Superiore, Piazza dei Cavalieri 7, 56126 Pisa, Italy.
authors.forename: Vincenzo
authors.initials: V
authors.lastname: Barone