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Transition state spectroscopy of the excited electronic states of Li–HF

AuthorsAguado, Alfredo ; Paniagua, Miguel; Sanz, Cristina; Roncero, Octavio
KeywordsLithium compounds
Hydrogen compounds
Excited states
Ab initio calculations
Molecular electronic states
Rotational-vibrational states
Potential energy surfaces
Digital simulation
[PACS] Potential energy surfaces for excited electronic states (atoms and molecules)
[PACS] Ab initio calculations (atoms and molecules)
[PACS] Molecular rotation, vibration, and vibration-rotation constants
Issue Date15-Nov-2003
PublisherAmerican Institute of Physics
CitationJournal of Chemical Physics 119(19): 10088 (2003)
AbstractIn this work the LiHF(A,B,B' <-- X) electronic spectrum is simulated and compared with the experimental one obtained by Hudson et al. [J. Chem. Phys. 113, 9897 (2000)]. High level ab initio calculations of three 2A' and one 2A'' electronic states have been performed using a new atomic basis set and for a large number of nuclear configurations (about 6000). Four analytic global potential energy surfaces have been fitted. The spectrum involved very excited rovibrational states, close to the first dissociation limit, at high total angular momentum. Two different methods have been used, one based on bound state and the second one on wave packet calculations. Different alternatives have been used to simulate the relatively high temperatures involved. The agreement obtained with the experimental spectrum is very good allowing a very simple assignment of the peaks. They are due to bending progressions on the three excited electronic states. A simple model is used in which only rotational degrees of freedom are included, which simulates the spectrum in excellent agreement with the experimental one, providing a nice physical interpretation. Moreover, the remaining theoretical/experimental discrepancies have been attributed to nonadiabatic effects through the extension of this model to a diabatic representation of excited coupled electronic states.
Description16 pages, 14 figures, 5 tables.-- PACS nrs.: 31.50.Df; 31.15.Ar; 33.15.Mt.
Publisher version (URL)http://dx.doi.org/10.1063/1.1618223
Appears in Collections:(CFMAC-IFF) Artículos
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