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The Discrete Reaction Field approach for calculating solvent effects

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Book cover Solvation Effects on Molecules and Biomolecules

Part of the book series: Challenges and Advances in Computational Chemistry and Physics ((COCH,volume 6))

Abstract

We present here the discrete reaction field (DRF) approach, which is an accurate and efficient model for studying solvent effects on spectra, chemical reactions, solute properties, etc. The DRF approach uses a polarizable force field, which is (apart from the short-range repulsion) based entirely on second-order perturbation theory, and therefore ensures the correct analytical form of model potentials. The individual interaction components are modeled independently from each other, in a rigorous and straightforward way. The required force field parameters result as much as possible from quantum-chemical calculations and on monomer properties, thereby avoiding undesired fitting of these parameters to empirical data.

Because the physical description is correct and consistent, the method allows for arbitrary division of a system into different subsystems, which may be described either on the quantum-mechanical (QM) or the molecular mechanics (MM) level, without significant loss of accuracy. This allows for performing fully MM molecular simulations (Monte Carlo, molecular dynamics), which can subsequently be followed by performing QM/MM calculations on a selected number of representative snapshots from these simulations. These QM/MM calculations then give directly the solvent effects on emission or absorption spectra, molecular properties, organic reactions, etc

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Authors and Affiliations

  1. Zernike Institute for Advanced Materials, Rijksuniversiteit Groningen, Nijenborgh 4, 9747 AG, Groningen, The Netherlands

    Piet Th. Van Duijnen

  2. Institució Catalana de Recerca i Estudis Avançats (ICREA), 08010 Barcelona, Spain and Institut de Química Computacional, Universitat de Girona, Campus Montilivi, 17071 Girona, Spain

    Marcel Swart

  3. Department of Chemistry, The Pennsylvania State University, University Park, PA 16802, USA

    Lasse Jensen

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  1. Piet Th. Van Duijnen
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  1. Instituto de Física, Universidade de São Paulo, São Paulo, 05315-970, Brazil

    Sylvio Canuto

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Van Duijnen, P.T., Swart, M., Jensen, L. (2008). The Discrete Reaction Field approach for calculating solvent effects. In: Canuto, S. (eds) Solvation Effects on Molecules and Biomolecules. Challenges and Advances in Computational Chemistry and Physics, vol 6. Springer, Dordrecht. https://doi.org/10.1007/978-1-4020-8270-2_3

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