New massively parallel linear-response coupled-cluster module in ACES III: Application to static polarisabilities of closed-shell molecules and oligomers and of open-shell radicals

Prakash Verma, Ajith Perera, Jorge A. Morales

Research output: Contribution to journalArticlepeer-review

2 Scopus citations

Abstract

Stemming from our implementation of parallel coupled-cluster (CC) capabilities for electron spin resonance properties [J. Chem. Phys. 139, 174103 (2013)], we present a new massively parallel linear response CC module within ACES III. Unlike alternative parallel CC modules, this general purpose module evaluates any type of first- and second-order CC properties of both closed- and open-shell molecules employing restricted, unrestricted and restricted-open-shell Hartree-Fock (HF) references. We demonstrate the accuracy and usefulness of this module through the calculation of static polarisabilities of large molecules. Closed-shell calculations are performed at the following levels: second-order many-body perturbation theory [MBPT(2)], CC with single- and double-excitations (CCSD), coupled-perturbed HF and density functional theory (DFT), and open-shell calculations at the unrestricted CCSD (UCSSD) one. Applications involve eight closed-shell organic-chemistry molecules (Set I), the first four members of the closed-shell thiophene oligomer series (Set II), and five open-shell radicals (Set III). In Set I, all calculated average polarisabilities agree reasonably well with experimental data. In Set II, all calculated average polarisabilities vs. the number of monomers show comparable values and saturation patterns and demonstrate that experimental polarisabilities may be inaccurate. In Set III, UCCSD perpendicular polarisabilities show a reasonable agreement with previous UCCSD(T) and restricted-open-shell-MBPT(2) values.

Original languageEnglish
Pages (from-to)547-561
Number of pages15
JournalMolecular Physics
Volume114
Issue number3-4
DOIs
StatePublished - Feb 16 2016

Keywords

  • Coupled-cluster theory
  • coupled-cluster response treatment of properties
  • massively parallel coupled-cluster implementations to evaluate properties
  • static dipole polarisabilities

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