Benchmark Quantum Mechanical Calculations of Vibrationally Resolved Cross Sections and Rate Constants on ab Initio Potential Energy Surfaces for the F + HD Reaction: Comparisons with Experiments

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• 作者：Dario De Fazio ; Simonetta Cavalli ; Vincenzo Aquilanti
• 刊名：Journal of Physical Chemistry A
• 出版年：2016
• 出版时间：July 14, 2016
• 年：2016
• 卷：120
• 期：27
• 页码：5288-5299
• 全文大小：545K
• 年卷期：0
• ISSN：1520-5215

文摘

Quantum scattering calculations within the time-independent approach in an extended interval of energies were performed for the title reaction on four ab initio potential energy surfaces. The calculated integral cross sections, vibrational branching ratios, and rate constants are compared with scattering experiments as well as with chemical kinetics rate data available for this system for both the HF and DF channels. The calculations on the CSZ (J. Chem. Phys. 2015, 142, 024303) and LWAL (J. Chem. Phys. 2007, 127, 174302) surfaces are in close agreement between them and reproduce satisfactorily the experimental measurements. The agreement with the experiments is improved with respect to calculations on the earlier SW (J. Chem. Phys. 1996, 104, 6515) and FXZ (J. Chem. Phys. 2008, 129, 011103) surfaces. The results presented here witness the remarkable progress made by quantum chemistry calculations in describing the interatomic interactions governing the dynamics and kinetics of this reaction. They also suggest that comparison with translationally and rotationally averaged experimental observables is not sufficient to assess the relative accuracy of highly accurate potential energy surfaces. The dynamics and kinetics calculations show that temperatures lower than 50 K or molecular beam energy spread below 1 meV must be reached to discriminate the accuracy of the LWAL and the CSZ surfaces.