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Similarity transformation of the electronic Schrödinger equation via Jastrow factorization

Published version
Peer-reviewed

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Article

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Abstract

jats:pBy expressing the electronic wavefunction in an explicitly correlated (Jastrow-factorized) form, a similarity-transformed effective Hamiltonian can be derived. The effective Hamiltonian is non-Hermitian and contains three-body interactions. The resulting ground-state eigenvalue problem can be solved projectively using a stochastic configuration-interaction formalism. Our approach permits the use of highly flexible Jastrow functions, which we show to be effective in achieving extremely high accuracy, even with small basis sets. Results are presented for the total energies and ionization potentials of the first-row atoms, achieving accuracy within a mH of the basis-set limit, using modest basis sets and computational effort.</jats:p>

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Keywords

51 Physical Sciences, 34 Chemical Sciences, 5102 Atomic, Molecular and Optical Physics, 3406 Physical Chemistry

Journal Title

Journal of Chemical Physics

Conference Name

Journal ISSN

0021-9606
1089-7690

Volume Title

151

Publisher

AIP Publishing

Rights

Publisher's own licence