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Published in

American Institute of Physics, The Journal of Chemical Physics, 24(155), 2021

DOI: 10.1063/5.0076888

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Cumulants as the variables of density cumulant theory: A path to Hermitian triples

Journal article published in 2021 by Jonathon P. Misiewicz, Justin M. Turney ORCID, Henry F. Schaefer ORCID
This paper was not found in any repository, but could be made available legally by the author.
This paper was not found in any repository, but could be made available legally by the author.

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Abstract

We study the combination of orbital-optimized density cumulant theory and a new parameterization of reduced density matrices in which the variables are the particle–hole cumulant elements. We call this combination OλDCT. We find that this new Ansatz solves problems identified in the previous unitary coupled cluster Ansatz for density cumulant theory: the theory is now free of near-zero denominators between occupied and virtual blocks, can correctly describe the dissociation of H2, and is rigorously size-extensive. In addition, the new Ansatz has fewer terms than the previous unitary Ansatz, and the optimal orbitals delivered by the exact theory are the natural orbitals. Numerical studies on systems amenable to full configuration interaction show that the amplitudes from the previous ODC-12 method approximate the exact amplitudes predicted by this Ansatz. Studies on equilibrium properties of diatomic molecules show that even with the new Ansatz, it is necessary to include triples to improve the accuracy of the method compared to orbital-optimized linearized coupled cluster doubles. With a simple iterative triples correction, OλDCT outperforms other orbital-optimized methods truncated at comparable levels in the amplitudes, as well as coupled cluster single and doubles with perturbative triples [CCSD(T)]. By adding four more terms to the cumulant parameterization, OλDCT outperforms CCSDT while having the same O(V5O3) scaling.