Perturbative universal state-selective correction for state-specific multi-reference coupled cluster methods

0464674 - ÚFCH JH 2017 RIV US eng J - Článek v odborném periodiku
Brabec, Jiří - Banik, Subrata - Kowalski, K. - Pittner, Jiří
Perturbative universal state-selective correction for state-specific multi-reference coupled cluster methods.
Journal of Chemical Physics. Roč. 145, č. 16 (2016), s. 164106. ISSN 0021-9606. E-ISSN 1089-7690
Grant CEP: GA MŠMT LH13117; GA ČR GAP208/11/2222
Grant ostatní: GA ČR(CZ) Ga15-00058Y
Institucionální podpora: RVO:61388955
Klíčová slova: INCOMPLETE MODEL SPACES * BRILLOUIN-WIGNER * HILBERT-SPACE
Kód oboru RIV: CF - Fyzikální chemie a teoretická chemie
Impakt faktor: 2.965, rok: 2016

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.
Trvalý link: http://hdl.handle.net/11104/0263479