Variational response-function formulation of vibrational circular dichroism - PubMed (original) (raw)

. 2011 Mar 14;13(10):4224-9.

doi: 10.1039/c0cp02230f. Epub 2011 Jan 31.

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Variational response-function formulation of vibrational circular dichroism

Sonia Coriani et al. Phys Chem Chem Phys. 2011.

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.

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