%0 Journal Article
%A Fazio, Dario De
%A Cavalli, Simonetta
%A Aquilanti, Vincenzo
%D 2016
%T 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
%U https://acs.figshare.com/articles/journal_contribution/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/3404827
%R 10.1021/acs.jpca.6b01471.s001
%2 https://ndownloader.figshare.com/files/5317936
%K dynamic
%K chemical kinetics rate data
%K Benchmark Quantum Mechanical Calculations
%K accuracy
%K LWAL
%K HF
%K HD
%K experiment
%K CSZ
%K kinetics calculations show
%K energy surfaces
%K DF
%K quantum chemistry calculations
%K beam energy spread
%K SW
%K ab
%K Phy
%K FXZ
%K Chem
%X 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.
%I ACS Publications