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Title: Vibrational spectra of Li{sub 3} first-excited electronic doublet state: Geometric-phase effects and statistical analysis

The authors present J = 0 calculations of all bound and pseudobound vibrational states of Li{sub 3} in its first-excited electronic doublet state by using a realistic double many-body expansion potential-energy surface and a minimum-residual filter diagonalization technique. The action of the system Hamiltonian on the wave function was evaluated by the spectral transform method in hyperspherical coordinates. Calculations of the vibrational spectra were carried out both without consideration and with consideration of geometric-phase effects. Dynamic Jahn-Teller and geometric-phase effects are found to play a significant role, while the calculated fundamental symmetric stretching frequency is larger by 8.3% than its reported experimental value of 326 cm{sup {minus}1}. From the neighbor-spacing distributions of the levels, it is observed that the title vibrational spectrum is quasi-regular in the short range and quasi-irregular in the long range. By the {Delta}{sub 2} standard defined in this article, it is found that the spectra are more nonuniform than those of the trough states for the ground electronic state.
Authors:
;
Publication Date:
OSTI Identifier:
20000638
Resource Type:
Journal Article
Resource Relation:
Journal Name: International Journal of Quantum Chemistry; Journal Volume: 75; Journal Issue: 2; Other Information: PBD: 1999
Research Org:
Univ. de Coimbra (PT)
Country of Publication:
United States
Language:
English
Subject:
66 PHYSICS; SPECTRA; VIBRATIONAL STATES; LITHIUM; MANY-BODY PROBLEM; MOLECULES; JAHN-TELLER EFFECT