Recoupling the singlet- and triplet-pairing channels in single-reference coupled cluster theory

Gomez, John A.; Henderson, Thomas M.; Scuseria, Gustavo E.

doi:10.1063/1.4963870

Recoupling the singlet- and triplet-pairing channels in single-reference coupled cluster theory

Journal Article · Tue Oct 04 00:00:00 EDT 2016 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4963870· OSTI ID:1465478

^[1]; ^[2]; Scuseria, Gustavo E. ^[2]

Rice Univ., Houston, TX (United States); Department of Chemistry, Rice University, Houston, Texas 77005, USA; Department of Physics and Astronomy, Rice University, Houston, Texas 77005, USA
Rice Univ., Houston, TX (United States)

It is well known that single-reference coupled cluster theory truncated to low orders of excitations gives the right answer for the right reason when systems are dominated by dynamical or weak correlation. Static or strong correlation is more problematic, causing often catastrophic breakdown of restricted coupled cluster. This failure can be remedied, e.g., by allowing symmetry breaking in the reference or taking a multi-reference approach, but poses an interesting theoretical problem, especially since many groups have found that simplifying the T₂ operator or the doubles amplitude equations gives better results. In singlet-paired coupled cluster, eliminating the triplet-pairing channel recovers reasonable qualitative behavior for strong correlation at the cost of a decreased description of dynamical correlation in weakly correlated situations. This behavior seems to hold for both closed- and open-shell systems. In this work, we explore the coupling of the singlet- and triplet-pairing channels of T₂ and attempt to recouple them in order to recover dynamical correlation without reintroducing catastrophic failure due to strong correlation. In the weakly correlated regime, these pairing channels are only weakly coupled, and a simple recoupling gives good results. Furthermore, as strong correlation dominates, the coupling strength between the singlet- and triplet-pairing channels increases, making it difficult to perturbatively recouple the singlet- and triplet-pairing channels in this regime.

View Accepted Manuscript (DOE)

Research Organization:: Rice Univ., Houston, TX (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC)

Grant/Contract Number:: FG02-04ER15523

OSTI ID:: 1465478

Alternate ID(s):: OSTI ID: 1328520

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 13 Vol. 145; ISSN JCPSA6; ISSN 0021-9606

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

Country of Publication:: United States

Language:: English

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Behind the success of modified coupled-cluster methods: addition by subtraction Rishi, Varun; Perera, Ajith; Bartlett, Rodney J. Molecular Physics, Vol. 117, Issue 17 https://doi.org/10.1080/00268976.2018.1492748	journal	July 2018
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