Gauge-origin independent calculation of magnetizabilities and rotational g tensors at the coupled-cluster level

Jürgen Gauss, Kenneth Ruud, Mihály Kállay

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Abstract

An implementation of the gauge-origin independent calculation of magnetizabilities and rotational g tensors at the coupled-cluster (CC) level is presented. The properties of interest are obtained as second derivatives of the energy with respect to the external magnetic field (in the case of the magnetizability) or with respect to magnetic field and rotational angular momentum (in the case of the rotational g tensor), while gauge-origin independence and fast basis-set convergence are ensured by using gauge-including atomic orbitals (London atomic orbitals) as well as their extension to treat rotational perturbations (rotational London atomic orbitals). The implementation within our existing CC analytic second-derivative code is described, focusing on the required modifications concerning integral evaluation and treatment of the unperturbed and perturbed two-particle density matrices. An extensive set of test calculations for LiH and BH (up to the full configuration-interaction limit), for a series of simple hydrides (HF, H2 O, N H3, and C H4) as well as the more challenging molecules CO, N2, and O3 [employing the CC singles and doubles (CCSD) and the CCSD approximation augmented by a perturbative treatment of triple excitations] demonstrates the importance of electron correlation for high-accuracy predictions of magnetizabilities and rotational g tensors.

Original languageEnglish
Article number074101
JournalJournal of Chemical Physics
Volume127
Issue number7
DOIs
Publication statusPublished - Aug 28 2007

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ASJC Scopus subject areas

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

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