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Title: Theoretical study of the dynamics and kinetics of the O + CS → CO + S chemical laser reaction, where CO shows a very high vibrational excitation
Author: Gamallo Belmonte, Pablo
Francia, Rafael
Martínez Ruiz, Rodrigo
Sayós Ortega, Ramón
González Pérez, Miguel
Keywords: Cinètica química
Reaccions químiques
Col·lisions (Física)
Química quàntica
Chemical kinetics
Chemical reactions
Collisions (Physics)
Quantum chemistry
Issue Date: 6-Nov-2012
Publisher: American Chemical Society
Abstract: The dynamics and kinetics of the O(3P) + CS(X1sigma+) → CO(X1sigma+) + S(3P) chemical laser reaction was studied theoretically in detail for the first time, as a function of collision energy (0.0388-2.0 eV) and rovibrational excitation of CS. This was made using the quasi-classical trajectory (QCT) method and employing the best ab initio analytical ground potential energy surface (1 3A' PES) available. A broad set of properties was determined, including scalar and vector properties, and the reaction mode. The behaviors observed and the considerable formation of OCS collision complexes were interpreted from some characteristics of the PES (early barrier, shallow minimum in the exit channel, and high exoergicity (mainly channeled into CO vibration; up to ≈81% of the available energy) and the kinematics. The QCT vibrational and rotational CO populations and the vector properties show a quite good agreement with experiments, but the QCT rate constants disagree. To better account for the kinetics, we performed CASPT2/aug-cc-pVTZ ab initio calculations on the stationary points along the minimum energy path of the ground and first excited (1 3A'') PESs. The transition state theory, which can be satisfactorily applied here, leads to rate constants (100-2000 K) that are quite close to the measured ones, where comparison is possible (150-300 K). We expect that these results will encourage further theoretical and experimental developments.
Note: Versió postprint del document publicat a:
It is part of: Journal of Physical Chemistry A, 2012, vol. 116, num. 48, p. 11783-11795
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ISSN: 1089-5639
Appears in Collections:Articles publicats en revistes (Ciència dels Materials i Química Física)

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