As a further development of the previously introduced a posteriori Universal State-Selective (USS) corrections [K. Kowalski, J. Chem. Phys. 134, 194107 (2011); J. Brabec et al., ibid. 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 full configuration interaction (FCI) limit is also investigated. Various forms of the USS and simplified diagonal USS corrections at the singles and doubles and perturbative triple 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 Brillouin-Wigner coupled cluster 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.
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21 March 2015
Research Article|
March 17 2015
Iterative universal state selective correction for the Brillouin-Wigner multireference coupled-cluster theory
Subrata Banik;
Subrata Banik
1J. Heyrovský Institute of Physical Chemistry,
Academy of Sciences of the Czech Republic
, CZ-18223 Prague 8, Czech Republic
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Lalitha Ravichandran;
Lalitha Ravichandran
1J. Heyrovský Institute of Physical Chemistry,
Academy of Sciences of the Czech Republic
, CZ-18223 Prague 8, Czech Republic
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Jiří Brabec;
Jiří Brabec
2Computational Research Division,
Lawrence Berkeley National Laboratory
, Berkeley, California 94720, USA
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Ivan Hubač;
Ivan Hubač
3Department of Chemical Physics, Faculty of Mathematics and Physics,
Comenius University
, 84215 Bratislava, Slovakia
4Institute of Physics,
Silesian University
, 74601 Opava, Czech Republic
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Karol Kowalski;
Karol Kowalski
a)
5William R. Wiley Environmental Molecular Sciences Laboratory, Battelle,
Pacific Northwest National Laboratory
, K8-91, P.O. Box 999, Richland, Washington 99352, USA
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Jiří Pittner
Jiří Pittner
b)
1J. Heyrovský Institute of Physical Chemistry,
Academy of Sciences of the Czech Republic
, CZ-18223 Prague 8, Czech Republic
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J. Chem. Phys. 142, 114106 (2015)
Article history
Received:
December 23 2014
Accepted:
February 25 2015
Citation
Subrata Banik, Lalitha Ravichandran, Jiří Brabec, Ivan Hubač, Karol Kowalski, Jiří Pittner; Iterative universal state selective correction for the Brillouin-Wigner multireference coupled-cluster theory. J. Chem. Phys. 21 March 2015; 142 (11): 114106. https://doi.org/10.1063/1.4914311
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