Electron Nuclear Dynamics of H+ + C2H2 at ELab = 30, 200, and 450 eV.

Abstract

We present a complete simplest-level electron nuclear dynamics (SLEND) investigation of H+ + C2H2 at collision energies ELab = 30, 200, and 450 eV. This reaction is relevant in astrophysics and provides a computationally feasible prototype for proton cancer therapy reactions. SLEND is a time-dependent, variational, direct, and nonadiabatic method that adopts a classical-mechanics description for the nuclei and a Thouless single-determinantal wave function for the electrons. We perform this study with our code PACE, which incorporates the One Electron Direct/Electron Repulsion Direct (OED/ERD) atomic integrals package developed by the Bartlett group. Current SLEND simulations with the 6-31G** basis set involves 2,646 trajectory calculations from 9 nonredundant, symmetry-inequivalent projectile-target orientations. For H+ + C2H2 at ELab = 30 eV, SLEND/6-31G** simulations predict one simple scattering process, and three reactive ones: C2H2 hydrogen substitution, C2H2 fragmentation into two CH moieties, and C2H2 fragmentation into CHC and H moieties, respectively. We reveal and analyze the mechanisms of these processes through computer animations; this valuable chemical information is inaccessible by experiments. The SLEND/6-31G** scattering angle functions exhibit primary and secondary rainbow scattering features that vary with the projectile-target orientations and collision energies. SLEND/6-31G** predicts 1-electron-transfer (1-ET) integral cross sections at ELab = 30, 200, and 450 eV in good agreement with their experimental counterparts. SLEND/6-31-G** predicts 1-ET differential cross sections (DCSs) at ELab = 30 eV that agree well with their experimental counterparts over all the measured scattering angles. In addition, SLEND/6-31G** predicts 0-ET DCSs at ELab = 30 eV that agree well with their experimental counterparts at low scattering angles, but less satisfactorily at higher ones. Remarkably, both the 0- and 1-ET DCSs from SLEND/6-31G** exhibit distinct primary rainbow scattering signatures in excellent agreement with their experimentally inferred counterparts. Furthermore, both SLEND/6-31G** and the experiment indicate that the primary rainbow scattering angles from the 0- and 1-ET DCSs are identical (an unusual fact in proton-molecule collisions). Through these rainbow scattering predictions, SLEND has also validated a procedure to extract primary rainbow angles from structureless DCSs. We analyze the obtained theoretical results in comparison with available experimental data and discuss forthcoming developments in the SLEND method.