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Journal of Chemical Physics / Volume 131 / Issue 4 / ARTICLES / Theoretical Methods and Algorithms

J. Chem. Phys. 131, 044123 (2009); http://dx.doi.org/10.1063/1.3187527 (8 pages)

Heterogeneous conductorlike solvation model

Dejun Si and Hui Li

Department of Chemistry, University of Nebraska-Lincoln, Lincoln, Nebraska 68588, USA

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(Received 15 May 2009; accepted 7 July 2009; published online 27 July 2009)

A heterogeneous conductorlike solvation model (conductorlike screening model/conductorlike polarizable continuum model) that uses different local effective dielectrics for different portions of the solute cavity surface is implemented for quantum chemical Hartree–Fock and Kohn–Sham methods. A variational treatment is used to form the heterogeneous solvation operator, so a simple analytic expression of the energy gradients, which are vital for geometry optimization and molecular dynamics simulation, is derived and implemented. Using the new Fixed Points with Variable Areas surface tessellation scheme, continuous and smooth potential energy surfaces as well as analytic gradients are obtained for this heterogeneous model. Application of the heterogeneous solvation model to a realistic quantum model consisting of 101 atoms for the type-1 Cu center in rusticyanin shows that the desolvation due to protein burial can likely raise the reduction potential by ∼ 200 mV and, including the heterogeneity in geometry optimization, can likely affect the results by ∼ 2 kcal/mol or ∼ 70 mV.

© 2009 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. THEORY
    1. Heterogeneous COSMO and CPCM
    2. Hartree–Fock and Kohn–Sham methods
    3. Nuclear gradients
  3. COMPUTATIONAL METHODOLOGY
  4. RESULTS AND DISCUSSION
    1. Energy
    2. Gradients
    3. Type-1 Cu center
  5. CONCLUSION

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KEYWORDS and PACS

Keywords

biochemistry, density functional theory, HF calculations, molecular biophysics, molecular dynamics method, permittivity, potential energy surfaces, proteins, reaction kinetics theory, solvation, variational techniques

PACS

  • 82.30.Nr

    Association, addition, insertion, cluster formation

  • 87.15.R-

    Reactions and kinetics

  • 82.20.Kh

    Potential energy surfaces for chemical reactions

  • 82.20.Fd

    Collision theories; trajectory models

  • 82.20.Db

    Transition state theory and statistical theories of rate constants

  • 77.22.Ch

    Permittivity (dielectric function)

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.3187527

PUBLICATION DATA

ISSN

0021-9606 (print)  
1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef American Institute of Physics

For access to fully linked references, you need to log in.
    E. Cances, B. Mennucci, and J. Tomasi, J. Chem. Phys. 107, 3032 (1997)JCPSA6000107000008003032000001.

    H. Hoshi, M. Sakurai, Y. Inoue, and R. Chujo, J. Chem. Phys. 87, 1107 (1987)JCPSA6000087000002001107000001.

    L. Frediani, R. Cammi, S. Corni, and J. Tomasi, J. Chem. Phys. 120, 3893 (2004)JCPSA6000120000008003893000001.

    M. F. Iozzi, M. Cossi, R. Improta, N. Rega, and V. Barone, J. Chem. Phys. 124, 184103 (2006)JCPSA6000124000018184103000001.

    P. Su and H. Li, J. Chem. Phys. 130, 074109 (2009)JCPSA6000130000007074109000001.

    J. Baker, A. Kessi, and B. Delley, J. Chem. Phys. 105, 192 (1996)JCPSA6000105000001000192000001.

    T. H. Dunning, J. Chem. Phys. 90, 1007 (1989)JCPSA6000090000002001007000001
    N. B. Balabanov and K. A. Peterson, ibid. 123, 064107 (2005)JCPSA6000123000006064107000001.


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