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Title: Perturbations in vibrational diatomic spectra: Factorization of the molecular wave function

Abstract

The coupling between two electronic states of a diatomic molecule may lead to an erratic behaviour of the associated vibrational energies. An example is the homogeneous coupling between the valence b′ state and the Rydberg c′ state of the N{sub 2} molecule, both of symmetry {sup 1}Σ{sub u}{sup +}. The standard treatment of such a situation is to write the wave function as a sum of two Born-Oppenheimer products. It has recently been argued [L. S. Cederbaum, J. Chem. Phys. 138, 224110 (2013); N. I. Gidopoulos and E. K. U. Gross, Philos. Trans. R. Soc., A 372, 20130059 (2014)] that even in such a case the wave function should be representable as a single product, with an electronic factor depending parametrically on nuclear positions and a nuclear factor. We setup such a representation in the case of the perturbations in the N{sub 2} molecule.

Authors:
 [1]
  1. Institut des Sciences Moléculaires d’ Orsay (ISMO), Bât. 350, Univ. Paris-Sud (CNRS), 91405 Orsay, France and U.F.R. de Physique Fondamentale et Appliquée, Université Pierre et Marie Curie, 75321 Paris (France)
Publication Date:
OSTI Identifier:
22416138
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 7; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTRA; BORN-OPPENHEIMER APPROXIMATION; COUPLING; DISTURBANCES; FACTORIZATION; MOLECULES; NITROGEN; RYDBERG STATES; SYMMETRY; VALENCE; WAVE FUNCTIONS

Citation Formats

Lefebvre, R., E-mail: roland.lefebvre@u-psud.fr. Perturbations in vibrational diatomic spectra: Factorization of the molecular wave function. United States: N. p., 2015. Web. doi:10.1063/1.4907919.
Lefebvre, R., E-mail: roland.lefebvre@u-psud.fr. Perturbations in vibrational diatomic spectra: Factorization of the molecular wave function. United States. doi:10.1063/1.4907919.
Lefebvre, R., E-mail: roland.lefebvre@u-psud.fr. Sat . "Perturbations in vibrational diatomic spectra: Factorization of the molecular wave function". United States. doi:10.1063/1.4907919.
@article{osti_22416138,
title = {Perturbations in vibrational diatomic spectra: Factorization of the molecular wave function},
author = {Lefebvre, R., E-mail: roland.lefebvre@u-psud.fr},
abstractNote = {The coupling between two electronic states of a diatomic molecule may lead to an erratic behaviour of the associated vibrational energies. An example is the homogeneous coupling between the valence b′ state and the Rydberg c′ state of the N{sub 2} molecule, both of symmetry {sup 1}Σ{sub u}{sup +}. The standard treatment of such a situation is to write the wave function as a sum of two Born-Oppenheimer products. It has recently been argued [L. S. Cederbaum, J. Chem. Phys. 138, 224110 (2013); N. I. Gidopoulos and E. K. U. Gross, Philos. Trans. R. Soc., A 372, 20130059 (2014)] that even in such a case the wave function should be representable as a single product, with an electronic factor depending parametrically on nuclear positions and a nuclear factor. We setup such a representation in the case of the perturbations in the N{sub 2} molecule.},
doi = {10.1063/1.4907919},
journal = {Journal of Chemical Physics},
number = 7,
volume = 142,
place = {United States},
year = {Sat Feb 21 00:00:00 EST 2015},
month = {Sat Feb 21 00:00:00 EST 2015}
}