This paper describes and illustrates a way to construct multidimensional representations of reactive potential energy surfaces (PESs) by a multiconfiguration Shepard interpolation (MCSI) method based only on gradient information, that is, without using any Hessian information from electronic structure calculations. MCSI, which is called multiconfiguration molecular mechanics (MCMM) in previous articles, is a semiautomated method designed for constructing full-dimensional PESs for subsequent dynamics calculations (classical trajectories, full quantum dynamics, or variational transition state theory with multidimensional tunneling). The MCSI method is based on Shepard interpolation of Taylor series expansions of the coupling term of a electronically diabatic Hamiltonian matrix with the diagonal elements representing nonreactive analytical PESs for reactants and products. In contrast to the previously developed method, these expansions are truncated in the present version at the first order, and, therefore, no input of electronic structure Hessians is required. The accuracy of the interpolated energies is evaluated for two test reactions, namely, the reaction and the hydrogen atom abstraction from a model of -tocopherol by methyl radical. The latter reaction involves 38 atoms and a 108-dimensional PES. The mean unsigned errors averaged over a wide range of representative nuclear configurations (corresponding to an energy range of 19.5 kcal/mol in the former case and 32 kcal/mol in the latter) are found to be within 1 kcal/mol for both reactions, based on 13 gradients in one case and 11 in the other. The gradient-based MCMM method can be applied for efficient representations of multidimensional PESs in cases where analytical electronic structure Hessians are too expensive or unavailable, and it provides new opportunities to employ high-level electronic structure calculations for dynamics at an affordable cost.
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28 February 2010
Research Article|
February 23 2010
Gradient-based multiconfiguration Shepard interpolation for generating potential energy surfaces for polyatomic reactions Available to Purchase
Oksana Tishchenko;
Oksana Tishchenko
a)
Department of Chemistry and Supercomputing Institute,
University of Minnesota
, Minneapolis, Minnesota 55455-0431, USA
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Donald G. Truhlar
Donald G. Truhlar
b)
Department of Chemistry and Supercomputing Institute,
University of Minnesota
, Minneapolis, Minnesota 55455-0431, USA
Search for other works by this author on:
Oksana Tishchenko
a)
Department of Chemistry and Supercomputing Institute,
University of Minnesota
, Minneapolis, Minnesota 55455-0431, USA
Donald G. Truhlar
b)
Department of Chemistry and Supercomputing Institute,
University of Minnesota
, Minneapolis, Minnesota 55455-0431, USA
a)
Electronic mail: [email protected].
b)
Electronic mail: [email protected].
J. Chem. Phys. 132, 084109 (2010)
Article history
Received:
November 30 2009
Accepted:
January 19 2010
Citation
Oksana Tishchenko, Donald G. Truhlar; Gradient-based multiconfiguration Shepard interpolation for generating potential energy surfaces for polyatomic reactions. J. Chem. Phys. 28 February 2010; 132 (8): 084109. https://doi.org/10.1063/1.3310296
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