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Please use this identifier to cite or link to this item: http://hdl.handle.net/10261/14494
Title: Ab initio vibrational predissociation dynamics of He-I2(B) complex
Authors: Valdés, Álvaro; Prosmiti, Rita; Villarreal, Pablo; Delgado Barrio, Gerardo; Lemoine, Didier; Lepetit, Bruno
Keywords: Helium compounds
Coupled cluster calculations
Ab initio calculations
Potential energy functions
Vibrational states
Potential energy surfaces
Molecule-photon collisions
[PACS] Ab initio calculations (atoms and molecules)
[PACS] Coupled cluster theory (atoms and molecules)
[PACS] Diffuse molecular spectra; predissociation, photodissociation
[PACS] Vibrational analysis (molecular spectra)
[PACS] Molecular oscillator and band strengths, lifetimes, transition moments, and Franck-Condon factors
Issue Date: 29-Jun-2007
Publisher: American Institute of Physics
Citation: Journal of Chemical Physics 126(24): 244314 (2007)
Abstract: Three-dimensional quantum mechanical calculations on the vibrational predissociation dynamics of HeI2 B state complex are performed using a potential energy surface accurately fitted to unrestricted open-shell coupled cluster ab initio data, further enabling extrapolation for large I2 bond lengths. A Lanczos iterative method with an optimized complex absorbing potential is used to determine energies and lifetimes of the vibrationally predissociating He,I2(B,v') complex for v' ≤ 26 of I2 vibrational excitations. The calculated predissociating state energies agree with recent experimental results within 0.5 cm−1. This excellent agreement is remarkable since no adjustment was made with respect to the experiments. The present ab initio approach, however, shows its limitations in the fact that the computed lifetimes that are highly sensitive to subtle details of the potential energy surfaces such as anisotropy, are a factor of 1.5 larger than the available experimental data.
Description: 7 pages, 5 figures, 5 tables.-- PACS nrs.: 31.15.Ar; 31.15.Dv; 33.80.Gj; 33.20.Tp; 33.70.Ca.
Publisher version (URL): http://dx.doi.org/10.1063/1.2748404
URI: http://hdl.handle.net/10261/14494
DOI: 10.1063/1.2748404
ISSN: 0021-9606
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