Theoretical Study of the Ti-Cl Bond Cleavage Reaction in TiCl4
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Publication Date
2017-09Journal Title
Zeitschrift für Physikalische Chemie - International journal of research in physical chemistry and chemical physics
ISSN
0942-9352
Publisher
De Gruyter
Volume
231
Issue
9
Pages
1489-1506
Language
eng
Type
Article
This Version
VoR
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Nurkowski, D., Jasper, A., Akroyd, J., & Kraft, M. (2017). Theoretical Study of the Ti-Cl Bond Cleavage Reaction in TiCl4. Zeitschrift für Physikalische Chemie - International journal of research in physical chemistry and chemical physics, 231 (9), 1489-1506. https://doi.org/10.1515/zpch-2016-0866
Abstract
In this work the kinetics of the TiCl4 <=> TiCl3 + Cl reaction is studied theoretically. A variable-reaction coordinate transition-state theory (VRC-TST) is used to calculate the high-pressure limit rate coefficients. The interaction energy surface for the VRC-TST step is sampled directly at the CASPT2(6e,4o)/cc-pVDZ level of theory including an approximate treatment of the spin-orbit coupling. The pressure-dependence of the reaction in an argon bath gas is explored using the master equation in conjunction with the optimised VRC-TST transition-state number of states. The collisional energy transfer parameters for the TiCl 4-Ar system are estimated via a "one-dimensional minimisation" method and classical trajectories. The Ti-Cl bond dissociation energy is computed using a complete basis set extrapolation technique with cc-pVQZ and cc-pV5Z basis sets. Good quantitative agreement between the estimated rate constants and available literature data is observed. However, the fall-off behaviour of the model results is not seen in the current experimental data. Sensitivity analysis shows that the fall-off effect is insensitive to the choice of model parameters and methods. More experimental work and development of higher-level theoretical methods are needed to further investigate this discrepancy.
Keywords
ab initio, master equation, rate constant, TiCl4, VRC-TST
Relationships
Is supplemented by: https://doi.org/10.17863/CAM.4
Identifiers
External DOI: https://doi.org/10.1515/zpch-2016-0866
This record's URL: https://www.repository.cam.ac.uk/handle/1810/269649
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