Variational response-function formulation of vibrational circular dichroism

Sonia Coriani, Andreas J. Thorvaldsen, Kasper Kristensen, Poul Jørgensen

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

The atomic axial tensor (AAT) of vibrational circular dichroism is expressed as the frequency derivative at zero frequency of a linear response function for operators referencing a nuclear displacement and a magnetic field. This is used in the density matrix-based quasienergy derivative Lagrangian approach of Thorvaldsen et al. [J. Chem. Phys., 2008, 129, 214108] to express the AAT in a form where the need to solve response equations for the nuclear displacements is removed, significantly reducing the computation cost compared to existing formulations. The density matrix-based quasienergy derivative Lagrangian approach also allows us straightforwardly to use London atomic orbitals to remove the gauge-origin dependence and to account for the atomic orbitals' dependence on the nuclear coordinates. The formalism is entirely based on atomic-orbital density and integral matrices and therefore amenable to linear scaling for sufficiently sparse matrices and given a linearly scaling response solver.
Original languageEnglish
JournalPhysical Chemistry Chemical Physics
Volume13
Issue number10
Pages (from-to)4224-4229
ISSN1463-9076
DOIs
Publication statusPublished - 2011
Externally publishedYes

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