A variational formulation of the polarizable continuum model

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Issue Date
2010-07-07Author
Lipparini, Filippo
Scalmani, Giovanni
Mennucci, Benedetta
Cancès, Eric
Caricato, Marco
Frisch, Michael J.
Publisher
AIP Publishing
Type
Article
Article Version
Scholarly/refereed, publisher version
Rights
The following article appeared in Journal of Chemical Physics and may be found at http://scitation.aip.org/content/aip/journal/jcp/133/5/10.1063/1.3474570
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Show full item recordAbstract
Continuum solvation models are widely used to accurately estimate solvent effects on energy, structural and spectroscopic properties of complex molecular systems. The polarizable continuum model (PCM) is one of the most versatile among the continuum models because of the variety of properties that can be computed and the diversity of methods that can be used to describe the solute from molecular mechanics (MM) to sophisticated quantum mechanical (QM) post-self-consistent field methods or even hybrid QM/MM methods. In this contribution, we present a new formulation of PCM in terms of a free energy functional whose variational parameters include the continuum polarization (represented by the apparent surface charges), the solute’s atomic coordinates and—possibly—its electronic density. The problem of finding the optimized geometry of the (polarized) solute, with the corresponding self-consistent reaction field, is recast as the minimization of this free energy functional, simultaneously with respect to all its variables. The numerous potential applications of this variational formulation of PCM are discussed, including simultaneous optimization of solute’s geometry and polarization charges and extended Lagrangian dynamics. In particular, we describe in details the simultaneous optimization procedure and we include several numerical examples.
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Citation
Lipparini, F., Scalmani, G., Mennucci, B., Cancès, E., Caricato, M., & Frisch, M. J. (2010). A variational formulation of the polarizable continuum model. The Journal of chemical physics, 133(1), 014106.
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