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Article Dans Une Revue Journal of Chemical Physics Année : 2008

The H+3 rovibrational spectrum revisited with a global electronic potential energy surface

Luis Velilla
  • Fonction : Auteur
Bruno Lepetit
Alfredo Aguado
  • Fonction : Auteur
Miguel Paniagua
  • Fonction : Auteur

Résumé

In this paper, we have computed the rovibrational spectrum of the H+3 molecule using a new global potential energy surface, invariant under all permutations of the nuclei, that includes the long range electrostatic interactions analytically. The energy levels are obtained by a variational calculation using hyperspherical coordinates. From the comparison with available experimental results for low lying levels, we conclude that our accuracy is of the order of 0.1cm−1 for states localized in the vicinity of equilateral triangular configurations of the nuclei, and changes to the order of 1cm−1 when the system is distorted away from equilateral configurations. Full rovibrational spectra up to the H++H2dissociation energy limit have been computed. The statistical properties of this spectrum (nearest neighbor distribution and spectral rigidity) show the quantum signature of classical chaos and are consistent with random matrix theory. On the other hand, the correlation function, even when convoluted with a smoothing function, exhibits oscillations which are not described by random matrix theory. We discuss a possible similarity between these oscillations and the ones observed experimentally.
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Dates et versions

hal-00948346 , version 1 (18-02-2014)

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Citer

Luis Velilla, Bruno Lepetit, Alfredo Aguado, Alberto J. Beswick, Miguel Paniagua. The H+3 rovibrational spectrum revisited with a global electronic potential energy surface. Journal of Chemical Physics, 2008, 129, pp.084307. ⟨10.1063/1.2973629⟩. ⟨hal-00948346⟩
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