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Competition between adiabatic and nonadiabatic fragmentation pathways in the unimolecular decay of the ArI2(B) van der Waals complex

AuthorsRoncero, Octavio ; Buchachenko, Alexei A.; Lepetit, Bruno
Franck-Condon factors
Rotational-vibrational energy transfer
Vibrational states
Argon compounds
DIM calculations
Molecular electronic states
Perturbation theory
Molecule-photon collisions
[PACS] Rotational and vibrational energy transfer (atoms and molecules)
[PACS] Diffuse molecular spectra; predissociation, photodissociation
[PACS] Molecular oscillator and band strengths, lifetimes, transition moments, and Franck-Condon factors
[PACS] Molecular rotation, vibration, and vibration-rotation constants
[PACS] Perturbation theory (atoms and molecules)
[PACS] Vibrational analysis (molecular spectra)
Issue Date15-Jan-2005
PublisherAmerican Institute of Physics
CitationJournal of Chemical Physics 122(3): 034303 (2005)
AbstractThe competition between vibrational and electronic predissociations of the ArI2(B) van der Waals complex has been studied using several dynamical computational methods: exact quantum wave-packet propagation, time-dependent golden rule, and quasiclassical trajectory with quantum jumps model. Five electronic states are considered using recent three-dimensional coupled surfaces obtained with a perturbative diatoms-in-molecules method. Final vibrational and electronic populations, predissociation rates, and absorption spectra have been computed for I2(B,ν = 18–24) <-- I2(X,ν = 0) excitations within the complex. The contribution of vibrational predissociation into the total decay oscillates as a function of vibrational excitation due to intramolecular vibrational relaxation in a sparse-intermediate regime, which induces irregular variations of the total decay rate. Franck–Condon oscillations control the branching ratios of the individual electronic predissociation channels. However, since these oscillations are out of phase as a function of vibrational excitation, they have limited effect on the oscillatory behavior of the total predissociation rate. Comparison between exact quantum and perturbative golden rule calculations shows that vibrational predissociation has some impact on the electronic predissociation process and affects the final electronic distributions. On the contrary, vibrational product distributions are not significantly affected by the electronic predissociation. A classical description of the ArI2 dynamics provides an averaged picture of the competing predissociation processes, being better adapted for treating intermolecular vibrational relaxation in the statistical limit.
Description12 pages, 6 figures, 3 tables, 1 appendix.-- PACS nrs.: 34.50.Ez; 33.80.Gj; 33.70.Ca; 33.15.Mt; 31.15.Md; 33.20.Tp.
Publisher version (URL)http://dx.doi.org/10.1063/1.1832596
Appears in Collections:(CFMAC-IFF) Artículos
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