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

Jiri Brabec, Subrata Banik, Karol Kowalski, Jiří Pittner

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

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.

Original languageEnglish
Article number164106
JournalJournal of Chemical Physics
Volume145
Issue number16
DOIs
Publication statusPublished - 28-10-2016

Fingerprint

Electronic states
Invariance
Data storage equipment
Costs
preserving
invariance
projection
formalism
costs
formulations
orbitals
electronics

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Brabec, Jiri ; Banik, Subrata ; Kowalski, Karol ; Pittner, Jiří. / Perturbative universal state-selective correction for state-specific multi-reference coupled cluster methods. In: Journal of Chemical Physics. 2016 ; Vol. 145, No. 16.
@article{59ff5631828f43779f5c9df16344fb86,
title = "Perturbative universal state-selective correction for state-specific multi-reference coupled cluster methods",
abstract = "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.",
author = "Jiri Brabec and Subrata Banik and Karol Kowalski and Jiř{\'i} Pittner",
year = "2016",
month = "10",
day = "28",
doi = "10.1063/1.4965826",
language = "English",
volume = "145",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "16",

}

Perturbative universal state-selective correction for state-specific multi-reference coupled cluster methods. / Brabec, Jiri; Banik, Subrata; Kowalski, Karol; Pittner, Jiří.

In: Journal of Chemical Physics, Vol. 145, No. 16, 164106, 28.10.2016.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Perturbative universal state-selective correction for state-specific multi-reference coupled cluster methods

AU - Brabec, Jiri

AU - Banik, Subrata

AU - Kowalski, Karol

AU - Pittner, Jiří

PY - 2016/10/28

Y1 - 2016/10/28

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=84993953620&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84993953620&partnerID=8YFLogxK

U2 - 10.1063/1.4965826

DO - 10.1063/1.4965826

M3 - Article

VL - 145

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 16

M1 - 164106

ER -