Effective Hamiltonians derived from equation-of-motion coupled-cluster wave functions: Theory and application to the Hubbard and Heisenberg Hamiltonians

Pokhilko, Pavel; Krylov, Anna I.

doi:10.1063/1.5143318

Title: Effective Hamiltonians derived from equation-of-motion coupled-cluster wave functions: Theory and application to the Hubbard and Heisenberg Hamiltonians

Journal Article · Tue Mar 03 00:00:00 EST 2020 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5143318· OSTI ID:1602647

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Univ. of Southern California, Los Angeles, CA (United States)

Effective Hamiltonians, which are commonly used for fitting experimental observables, provide a coarse-grained representation of exact many-electron states obtained in quantum chemistry calculations; however, the mapping between the two is not trivial. In this contribution, we apply Bloch’s formalism to equation-of-motion coupled-cluster (EOM-CC) wave functions to rigorously derive effective Hamiltonians in the Bloch’s and des Cloizeaux’ forms. We report the key equations and illustrate the theory by application to systems with two or three unpaired electrons, which give rise to electronic states of covalent and ionic characters. We show that the Hubbard and Heisenberg Hamiltonians can be extracted directly from the so-obtained effective Hamiltonians. By establishing a quantitative connection between many-body states and simple models, the approach facilitates the analysis of the correlated wave functions. We propose a simple diagnostic for assessing the validity of the model space choice based on the overlaps between the target- and model-space states. Finally, artifacts affecting the quality of electronic structure calculations such as spin contamination are also discussed.

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Research Organization:: Univ. of Southern California, Los Angeles, CA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0018910

OSTI ID:: 1602647

Alternate ID(s):: OSTI ID: 1602591

Journal Information:: Journal of Chemical Physics, Vol. 152, Issue 9; Related Information: Supplementary information is available at https://aip.scitation.org/doi/suppl/10.1063/1.5143318; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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