Rovibrational energy levels of H3(+) with energies above the barrier to linearity

The H(3)(+) potential energy surface is sampled at 5900 geometries with the emphasis on the nonequilibrium and asymptotic points. Apart from the Born-Oppenheimer energy converged to the accuracy better than 0.02 cm(-1), the adiabatic and the leading relativistic corrections are computed at each geom...

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Veröffentlicht in:The Journal of chemical physics 2009-07, Vol.131 (2), p.024105-024105
Hauptverfasser: Bachorz, Rafał A, Cencek, Wojciech, Jaquet, Ralph, Komasa, Jacek
Format: Artikel
Sprache:eng
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Zusammenfassung:The H(3)(+) potential energy surface is sampled at 5900 geometries with the emphasis on the nonequilibrium and asymptotic points. Apart from the Born-Oppenheimer energy converged to the accuracy better than 0.02 cm(-1), the adiabatic and the leading relativistic corrections are computed at each geometry. To represent analytically the potential energy surface, the parameters of a power series are determined by fitting to the computed energy points. Possible choice of nuclear masses simulating the nonadiabatic effects in solving the nuclear Schrodinger equation is analyzed. A set of theoretically predicted rovibrational transitions is confronted with the experimental data in the 10,700-13,700 cm(-1) window of the spectra.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.3167795