In this work we present analytical expressions for Hamiltonian matrix elements with spherically symmetric, explicitly correlated Gaussian basis functions with complex exponential parameters for an arbitrary number of particles. The expressions are derived using the formalism of matrix differential calculus. In addition, we present expressions for the energy gradient that includes derivatives of the Hamiltonian integrals with respect to the exponential parameters. The gradient is used in the variational optimization of the parameters. All the expressions are presented in the matrix form suitable for both numerical implementation and theoretical analysis. The energy and gradient formulas have been programed and used to calculate ground and excited states of the He atom using an approach that does not involve the Born-Oppenheimer approximation.
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14 June 2006
Research Article|
June 13 2006
Matrix elements of -particle explicitly correlated Gaussian basis functions with complex exponential parameters
Sergiy Bubin;
Sergiy Bubin
a)
Department of Physics,
University of Arizona
, Tucson, Arizona 85721 and Department of Chemistry, University of Arizona
, Tucson, Arizona 85721
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Ludwik Adamowicz
Ludwik Adamowicz
Department of Physics,
University of Arizona
, Tucson, Arizona 85721 and Department of Chemistry, University of Arizona
, Tucson, Arizona 85721
Search for other works by this author on:
a)
Electronic mail: bubin@email.arizona.edu
J. Chem. Phys. 124, 224317 (2006)
Article history
Received:
September 29 2005
Accepted:
April 19 2006
Citation
Sergiy Bubin, Ludwik Adamowicz; Matrix elements of -particle explicitly correlated Gaussian basis functions with complex exponential parameters. J. Chem. Phys. 14 June 2006; 124 (22): 224317. https://doi.org/10.1063/1.2204605
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