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Perturbative universal state-selective correction for state-specific multi-reference coupled cluster methods
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SYSNO ASEP 0464674 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title Perturbative universal state-selective correction for state-specific multi-reference coupled cluster methods Author(s) Brabec, Jiří (UFCH-W) RID, ORCID
Banik, Subrata (UFCH-W)
Kowalski, K. (US)
Pittner, Jiří (UFCH-W) RID, ORCIDSource Title Journal of Chemical Physics. - : AIP Publishing - ISSN 0021-9606
Roč. 145, č. 16 (2016), s. 164106Number of pages 11 s. Language eng - English Country US - United States Keywords INCOMPLETE MODEL SPACES ; BRILLOUIN-WIGNER ; HILBERT-SPACE Subject RIV CF - Physical ; Theoretical Chemistry R&D Projects LH13117 GA MŠMT - Ministry of Education, Youth and Sports (MEYS) GAP208/11/2222 GA ČR - Czech Science Foundation (CSF) Institutional support UFCH-W - RVO:61388955 UT WOS 000387586200011 EID SCOPUS 84993953620 DOI 10.1063/1.4965826 Annotation In this work, we report an extension of our previous development of the universal state-selective (USS) multireference coupled-cluster (MRCC) formalism. It was shown [Brabec et al., J. Chem. Phys. 136, 124102 (2012)] and [Banik et al., J. Chem. Phys. 142, 114106 (2015)] that the USS(2) approach significantly improves the accuracy of Brillouin-Wigner and Mukherjee MRCC formulations, however, the numerical and storage costs associated with calculating highly excited intermediates pose a significant challenge, which can restrict the applicability of the USS(2) method. Therefore, we introduce a perturbative variant of the USS(2) approach (USS(pt)), which substantially reduces numerical overhead of the full USS(2) correction while preserving its accuracy. Since the new USS(pt) implementation calculates the triple and quadruple projections in on-the-fly manner, the memory bottleneck associated with the need of storing expensive recursive intermediates is entirely eliminated. On the example of several benchmark systems, we demonstrate accuracies of USS(pt) and USS(2) approaches and their efficiency in describing quasidegenerate electronic states. It is also shown that the USS(pt) method significantly alleviates problems associated with the lack of invariance of MRCC theories upon the rotation of active orbitals. Workplace J. Heyrovsky Institute of Physical Chemistry Contact Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Year of Publishing 2017
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