Journal article
Variational response-function formulation of vibrational circular dichroism
Dipartimento di Scienze Chimiche e Farmaceutiche, Università degli Studi di Trieste, Via L. Giorgieri 1, I-34127 Trieste, Italy. coriani@units.it1
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.
Language: | English |
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Publisher: | The Royal Society of Chemistry |
Year: | 2011 |
Pages: | 4224-4229 |
ISSN: | 14639084 and 14639076 |
Types: | Journal article |
DOI: | 10.1039/c0cp02230f |
ORCIDs: | Coriani, Sonia and Jørgensen, Poul |