Numerically stable optimized effective potential method with balanced Gaussian basis sets

Heßelmann A, Götz A, Della Sala F, Görling A (2007)


Publication Type: Journal article, Original article

Publication year: 2007

Journal

Original Authors: Heßelmann A., Götz A.W., Della Sala F., Görling A.

Publisher: American Institute of Physics (AIP)

Book Volume: 127

Article Number: 054102

Journal Issue: 5

DOI: 10.1063/1.2751159

Abstract

A solution to the long-standing problem of developing numerically stable optimized effective potential (OEP) methods based on Gaussian basis sets is presented by introducing an approach consisting of an exact exchange OEP method with an accompanying construction and balancing scheme for the involved auxiliary and orbital Gaussian basis sets that is numerically stable and that properly represents an exact exchange Kohn-Sham method. The method is a purely analytical method that does not require any numerical grid, scales like Hartree-Fock or B3LYP procedures, is straightforward to implement, and is easily generalized to take into account orbital-dependent density functionals other than the exact exchange considered in this work. Thus, the presented OEP approach opens the way to the development and application of novel orbital-dependent exchange-correlation functionals. It is shown that adequately taking into account the continuum part of the Kohn-Sham orbital spectrum is crucial for numerically stable Gaussian basis set OEP methods. Moreover, it is mandatory to employ orbital basis sets that are converged with respect to the used auxiliary basis representing the exchange potential. OEP calculations in the past often did not meet the latter requirement and therefore may have led to erroneously low total energies. © 2007 American Institute of Physics.

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How to cite

APA:

Heßelmann, A., Götz, A., Della Sala, F., & Görling, A. (2007). Numerically stable optimized effective potential method with balanced Gaussian basis sets. Journal of Chemical Physics, 127(5). https://doi.org/10.1063/1.2751159

MLA:

Heßelmann, Andreas, et al. "Numerically stable optimized effective potential method with balanced Gaussian basis sets." Journal of Chemical Physics 127.5 (2007).

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