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Title: Iterative universal state selective correction for the Brillouin-Wigner multireference coupled-cluster theory

As a further development of the previously introduced a posteriori Universal State-Selective (USS) corrections [K. Kowalski, J. Chem. Phys. 134, 194107 (2011)] and [Brabec et al., J. Chem. Phys., 136, 124102 (2012)], we suggest an iterative form of the USS correction by means of correcting effective Hamiltonian matrix elements. We also formulate USS corrections via the left Bloch equations. The convergence of the USS corrections with excitation level towards the FCI limit is also investigated. Various forms of the USS and simplified diagonal USSD corrections at the SD and SD(T) levels are numerically assessed on several model systems and on the ozone and tetramethyleneethane molecules. It is shown that the iterative USS correction can successfully replace the previously developed a posteriori BWCC size-extensivity correction, while it is not sensitive to intruder states and performs well also in other cases when the a posteriori one fails, like e.g. for the asymmetric vibration mode of ozone.
Authors:
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Publication Date:
OSTI Identifier:
1182861
Report Number(s):
PNNL-SA-107175
48604; KP1704020
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics, 142(15):Article No. 114106
Research Org:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
Brillouin-Wigner; multireference; coupled-cluster theory; ozone; tetramethyleneethane; Environmental Molecular Sciences Laboratory