title: Analytical gradients for MP2, double hybrid functionals, and TD-DFT with polarizable embedding described by fluctuating charges.
abstract: A polarizable quantum mechanics (QM)/ molecular mechanics (MM) approach recently developed for Hartree-Fock (HF) and Kohn-Sham (KS) methods has been extended to energies and analytical gradients for MP2, double hybrid functionals, and TD-DFT models, thus allowing the computation of equilibrium structures for excited electronic states together with more accurate results for ground electronic states. After a detailed presentation of the theoretical background and of some implementation details, a number of test cases are analyzed to show that the polarizable embedding model based on fluctuating charges (FQ) is remarkably more accurate than the corresponding electronic embedding based on a fixed charge (FX) description. In particular, a set of electronegativities and hardnesses has been optimized for interactions between QM and FQ regions together with new repulsion-dispersion parameters. After validation of both the numerical implementation and of the new parameters, absorption electronic spectra have been computed for representative model systems including vibronic effects. The results show remarkable agreement with full QM computations and significant improvement with respect to the corresponding FX results. The last part of the article provides some hints about computation of solvatochromic effects on absorption spectra in aqueous solution as a function of the number of FQ water molecules and on the use of FX external shells to improve the convergence of the results. © 2015 The Authors. Journal of Computational Chemistry Published by Wiley Periodicals, Inc.
authors.affiliation: Istituto Italiano Di Tecnologia (IIT), Compunet, via Morego, 30 I-16163 Genova, Italy and Scuola Normale Superiore, Piazza Dei Cavalieri, 7 I-56126, Pisa, Italy.
authors.forename: Ivan
authors.initials: I
authors.lastname: Carnimeo
authors.affiliation: Dipartimento di Chimica e Chimica Industriale, Università di Pisa, via Moruzzi, 13, I-56124, Pisa, Italy.
authors.forename: Chiara
authors.initials: C
authors.lastname: Cappelli
authors.affiliation: Scuola Normale Superiore, Piazza dei Cavalieri, 7 I-56126, Pisa, Italy.
authors.forename: Vincenzo
authors.initials: V
authors.lastname: Barone
mesh_terms: D000096:Acetone / Q000737:chemistry; D004583:Electrons; D005559:Formamides / Q000737:chemistry; D011725:Pyridines / Q000737:chemistry; D011743:Pyrimidines / Q000737:chemistry; D011789:Quantum Theory; D055672:Static Electricity; D014867:Water / Q000737:chemistry
chemical_list: D005559:Formamides; D011725:Pyridines; D011743:Pyrimidines; D014867:Water; D000096:Acetone; C031066:formamide; C030986:pyrimidine; C023666:pyridine
keywords: DFT; MP2; TD-DFT; excited states; fluctuating charges; gradients; quantum mechanics/molecular mechanics