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Efficient calculation of the energy of a molecule in an arbitrary electric field

Publication ,  Journal Article
Pulay, P; Janowski, T
Published in: International Journal of Quantum Chemistry
July 9, 2009

In thermodynamic (e.g., Monte Carlo) simulations with electronic embedding, the energy of the active site or solute must be calculated for millions of configurations of the environment (solvent or protein matrix) to obtain reliable statistics. This precludes the use of accurate but expensive ab initio and density functional techniques. Except for the immediate neighbors, the effect of the environment is electrostatic. We show that the energy of a molecule in the irregular field of the environment can be determined very efficiently by expanding the electric potential in known functions, and precalculating the first and second order response of the molecule to the components of the potential. These generalized multipole moments and polarizabilities allow the calculation of the energy of the system without further ab initio calculations. Several expansion functions were explored: polynomials, distributed inverse powers, and sine functions. The latter provide the numerically most stable fit but require new types of integrals. Distributed inverse powers can be simulated using dummy atoms, and energies calculated this way provide a very good approximation to the actual energies in the field of the environment. ©2009 Wiley Periodicals, Inc.

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Published In

International Journal of Quantum Chemistry

DOI

EISSN

1097-461X

ISSN

0020-7608

Publication Date

July 9, 2009

Volume

109

Issue

10

Start / End Page

2113 / 2120

Related Subject Headings

  • Chemical Physics
  • 0307 Theoretical and Computational Chemistry
  • 0306 Physical Chemistry (incl. Structural)
 

Citation

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Pulay, P., & Janowski, T. (2009). Efficient calculation of the energy of a molecule in an arbitrary electric field. International Journal of Quantum Chemistry, 109(10), 2113–2120. https://doi.org/10.1002/qua.22064
Pulay, P., and T. Janowski. “Efficient calculation of the energy of a molecule in an arbitrary electric field.” International Journal of Quantum Chemistry 109, no. 10 (July 9, 2009): 2113–20. https://doi.org/10.1002/qua.22064.
Pulay P, Janowski T. Efficient calculation of the energy of a molecule in an arbitrary electric field. International Journal of Quantum Chemistry. 2009 Jul 9;109(10):2113–20.
Pulay, P., and T. Janowski. “Efficient calculation of the energy of a molecule in an arbitrary electric field.” International Journal of Quantum Chemistry, vol. 109, no. 10, July 2009, pp. 2113–20. Scopus, doi:10.1002/qua.22064.
Pulay P, Janowski T. Efficient calculation of the energy of a molecule in an arbitrary electric field. International Journal of Quantum Chemistry. 2009 Jul 9;109(10):2113–2120.
Journal cover image

Published In

International Journal of Quantum Chemistry

DOI

EISSN

1097-461X

ISSN

0020-7608

Publication Date

July 9, 2009

Volume

109

Issue

10

Start / End Page

2113 / 2120

Related Subject Headings

  • Chemical Physics
  • 0307 Theoretical and Computational Chemistry
  • 0306 Physical Chemistry (incl. Structural)