Han Huixian, Alday Benjamin, Shuman Nicholas S, Wiens Justin P, Troe Jürgen, Viggiano Albert A, Guo Hua
Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, USA.
Air Force Research Laboratory, Space Vehicles Directorate, Kirtland Air Force Base, New Mexico 87117, USA.
Phys Chem Chem Phys. 2016 Nov 16;18(45):31064-31071. doi: 10.1039/c6cp05867a.
To provide a deeper understanding of the kinetics of electron attachment to CF, the six-dimensional potential energy surfaces of both CF and CF were developed by fitting ∼3000 ab initio points per surface at the AE-CCSD(T)-F12a/AVTZ level using the permutation invariant polynomial-neural network (PIP-NN) approach. The fitted potential energy surfaces for CF and CF had root mean square fitting errors relative to the ab initio calculations of 1.2 and 1.8 cm, respectively. The main active mode for the crossing between the two potential energy surfaces was identified as the umbrella bending mode of CF in C symmetry. The lowest energy crossing point is located at R = 1.306 Å and θ = 113.6° with the energy of 0.051 eV above the minimum of the CF electronic surface. This value is only slightly larger than the experimental data 0.026 ± 0.01 eV determined by kinetic modeling of electron attachment to CF. The small discrepancy between the theoretical and experimentally measured values is analyzed.
