The accuracies of effective interactions in downfolding coupled-cluster approaches for small-dimensionality active spaces

Kowalski, Karol; Peng, Bo; Bauman, Nicholas P.

doi:10.1063/5.0207534

The accuracies of effective interactions in downfolding coupled-cluster approaches for small-dimensionality active spaces

Journal Article · Tue Jun 11 00:00:00 EDT 2024 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/5.0207534· OSTI ID:2499514

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Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Here, this paper evaluates the accuracy of the Hermitian form of the downfolding procedure using the double unitary coupled cluster (DUCC) ansatz on the benchmark systems of linear chains of hydrogen atoms, H6 and H8. The computational infrastructure employs the occupation-number-representation codes to construct the matrix representation of arbitrary second-quantized operators, allowing for the exact representation of exponentials of various operators. The tests demonstrate that external amplitudes from standard single-reference coupled cluster methods that sufficiently describe external (out-of-active-space) correlations reliably parameterize the Hermitian downfolded effective Hamiltonians in the DUCC formalism. The results show that this approach can overcome the problems associated with losing the variational character of corresponding energies in the corresponding SR-CC theories.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 2499514

Report Number(s):: PNNL-SA--196097

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 22 Vol. 160; ISSN 0021-9606

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

Country of Publication:: United States

Language:: English

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