title: Variational response-function formulation of vibrational circular dichroism.
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.
authors.affiliation: Dipartimento di Scienze Chimiche e Farmaceutiche, Università degli Studi di Trieste, Via L. Giorgieri 1, I-34127 Trieste, Italy. coriani@units.it
authors.forename: Sonia
authors.initials: S
authors.lastname: Coriani
authors.forename: Andreas J
authors.initials: AJ
authors.lastname: Thorvaldsen
authors.forename: Kasper
authors.initials: K
authors.lastname: Kristensen
authors.forename: Poul
authors.initials: P
authors.lastname: Jørgensen