Amb motiu del tancament d'estiu, la validació de documents es reprendrà a partir del 28 d'agost de 2026. Disculpeu les molèsties.
Con motivo del cierre de verano, la validación de documentos se reanudará a partir del 28 de agosto de 2026. Disculpad las molestias
Due to the summer closure, document validation will resume starting August 28, 2026. We apologize for any inconvenience.

Files

617283.pdf (2.19 MB)

Document type

Article

Version

Accepted version

Publication date

2012-11-06

All rights reserved

Please use this identifier to cite or link to this item: https://hdl.handle.net/2445/163617

Theoretical study of the dynamics and kinetics of the O + CS → CO + S chemical laser reaction, where CO shows a very high vibrational excitation

Journal Title

Authors

Director/Tutor

Journal ISSN

Volume Title

Related resource

https://doi.org/10.1021/jp306218z

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.

Subject

Cinètica química, Reaccions químiques, Col·lisions (Física), Química quàntica

Subject (English)

Chemical kinetics, Chemical reactions, Collisions (Physics), Quantum chemistry

Citation

Collections

Articles publicats en revistes (Ciència dels Materials i Química Física)

Citation

GAMALLO BELMONTE, Pablo, et al. Theoretical study of the dynamics and kinetics of the O + CS → CO + S chemical laser reaction, where CO shows a very high vibrational excitation. Journal of Physical Chemistry A. 2012. Vol. 116, num. 48, pags. 11783-11795. ISSN 1089-5639. [consulted: 13 of August of 2026]. Available at: https://hdl.handle.net/2445/163617

Export metadata

JSON - METS

Share record