Published in

American Institute of Physics, The Journal of Chemical Physics, 9(121), p. 4043

DOI: 10.1063/1.1778711

Links

Tools

Export citation

Search in Google Scholar

A quasidegenerate formulation of the second order n-electron valence state perturbation theory approach

Journal article published in 2004 by Celestino Angeli ORCID, Stefano Borini, Mirko Cestari, Renzo Cimiraglia
This paper was not found in any repository, but could be made available legally by the author.
This paper was not found in any repository, but could be made available legally by the author.

Full text: Unavailable

Green circle
Preprint: archiving allowed
Green circle
Postprint: archiving allowed
Orange circle
Published version: archiving restricted
Data provided by SHERPA/RoMEO

Abstract

The n-electron valence state perturbation theory (NEVPT) is reformulated in a quasidegenerate (QD) approach. The new theory allows the treatment of cases where the proximity of the energies causes artifacts in the zero order description. Problems of quasidegeneration are relevant in the dynamics involving regions at avoided crossings (or conical intersections) and in spectroscopy where the energies and oscillator strengths can be strongly influenced by the mixing of states of different nature. Two test cases are analyzed concerning (a) the ionic-neutral avoided crossing in LiF and (b) the valence/Rydberg mixing in the excited states of ethene. The QD-NEVPT2 is shown to be a useful tool for such systems.