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).
2012
File in questo prodotto:
Non ci sono file associati a questo prodotto.
Pubblicazioni consigliate

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11368/2620644
 Avviso

Registrazione in corso di verifica.
La registrazione di questo prodotto non è ancora stata validata in ArTS.

Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus ND
  • ???jsp.display-item.citation.isi??? ND
social impact