The Journal of Chemical Physics

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

Karol Kowalski, Bo Peng, Nicholas P. Bauman

Published Jun 11, 2024• 5 citations

Abstract

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.

DOI: 10.1063/5.0207534

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