An alternative formulation of the atomic axial tensor (AAT) of vibrational circular dichroism as the frequency derivative at zero frequency of a linear response function for operators referencing a nuclear displacement and a magnetic field is presented [1]. When used in the density matrix-based quasienergy derivative Lagrangian approach of Thorvaldsen et al.[2], this allows 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 formalism also straightforwardly accounts for all contributions arising from the use of perturbation dependent basis sets. It is also expected to pave the way for gauge-origin independent implementations of VCD within non-variational wave-function theories. References [1] S. Coriani , A. J. Thorvaldsen, K. Kristensen and Poul Jørgensen, Phys. Chem. Chem. Phys.13 4224-4229 (2011) [2] A. Thorvaldsen, K. Ruud, K. Kristensen, P. Jørgensen and S. Coriani, J. Chem. Phys. 129 214108 (2008).
Variational response-function formulation of vibrational circular dichroism
CORIANI, Sonia
2012-01-01
Abstract
An alternative formulation of the atomic axial tensor (AAT) of vibrational circular dichroism as the frequency derivative at zero frequency of a linear response function for operators referencing a nuclear displacement and a magnetic field is presented [1]. When used in the density matrix-based quasienergy derivative Lagrangian approach of Thorvaldsen et al.[2], this allows 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 formalism also straightforwardly accounts for all contributions arising from the use of perturbation dependent basis sets. It is also expected to pave the way for gauge-origin independent implementations of VCD within non-variational wave-function theories. References [1] S. Coriani , A. J. Thorvaldsen, K. Kristensen and Poul Jørgensen, Phys. Chem. Chem. Phys.13 4224-4229 (2011) [2] A. Thorvaldsen, K. Ruud, K. Kristensen, P. Jørgensen and S. Coriani, J. Chem. Phys. 129 214108 (2008).Pubblicazioni consigliate
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