Variational properties of the discrete variable representation: Discrete variable representation via effective operators

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Abstract

A variational finite basis representation/discrete variable representation (FBR/DVR) Hamiltonian operator has been introduced. By calculating its matrix elements exactly one obtains, depending on the choice of the basis set, either a variational FBR or a variational DVR. The domain of grid points on which the FBR/DVR is variational has been shown to consist of the subsets of the set of grid points one obtains by diagonalizing commuting variational basis representations of the coordinate operators. The variational property implies that the optimal of the subsets of a fixed number of points, i.e., the subset which gives the possible highest accuracy eigenpairs, gives the DVR of the smallest trace. The symmetry properties of the variational FBR/DVR Hamiltonian operator are analyzed and methods to incorporate symmetry into FBR/DVR calculations are discussed. It is shown how the Fourier-basis FBR/DVR suitable to solving periodic systems arise within the theory presented. Numerical examples are given to illustrate the theoretical results. The use of variational effective Hamiltonian and coordinate operators has been instrumental in this study. They have been introduced in a novel way by exploiting quasi-Hermiticity.

Original languageEnglish
Article number064118
JournalJournal of Chemical Physics
Volume137
Issue number6
DOIs
Publication statusPublished - Aug 14 2012

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ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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