Journal
ZEITSCHRIFT FUR PHYSIKALISCHE CHEMIE-INTERNATIONAL JOURNAL OF RESEARCH IN PHYSICAL CHEMISTRY & CHEMICAL PHYSICS
Volume 231, Issue 9, Pages 1489-1506Publisher
WALTER DE GRUYTER GMBH
DOI: 10.1515/zpch-2016-0866
Keywords
ab initio; master equation; rate constant; TiCl4; VRC-TST
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Funding
- Huntsman Pigments and Additives
- EPSRC [EP/J500380/1]
- National Research Foundation (NRF), Prime Minister's Office, Singapore under its Campus for Research - Excellence and Technological Enterprise (CREATE) programme
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences [DE-AC04-94AL85000]
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In this work the kinetics of the TiCl4 reversible arrow 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 TiCl4 -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.
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