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Theoretical Study of the Ti-Cl Bond Cleavage Reaction in TiCl4

Published version
Peer-reviewed

Type

Article

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Authors

Nurkowski, D 
Jasper, AW 

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.

Description

Keywords

ab initio, master equation, rate constant, TiCl4, VRC-TST

Journal Title

Zeitschrift für Physikalische Chemie - International journal of research in physical chemistry and chemical physics

Conference Name

Journal ISSN

0942-9352
2196-7156

Volume Title

231

Publisher

De Gruyter
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