Charge Transfer Processes for H + H2+ Reaction Employing Coupled 3D Wavepacket Approach on Beyond Born-Oppenheimer Based Ab Initio Constructed Diabatic Potential Energy Surfaces

The dynamics of the H + H-2(+) reaction has been analyzed from the electronically first excited state of diabatic potential energy surfaces constructed by employing the Beyond Born-Oppenheimer theory [J. Chem. Phys. 2014, 141, 204306]. We have employed the coupled 3D time-dependent wavepacket formalism in hyperspherical coordinates for multisurface reactive scattering problems. To be specific, the charge transfer processes have been investigated extensively by calculating state-to-state as well as total reaction probabilities and integral cross sections, when the reaction process is initiated from the first excited electronic state (2(1)A'). We have depicted the convergence profiles of reaction probabilities for the competing charge transfer processes, namely, reactive charge transfer (RCT) and nonreactive charge transfer (NRCT) processes for different total energies with respect to total angular momentum, J. Total and state-to-state integral cross sections are calculated as a function of total energy for the initial rovibrational state, namely, v = 0, j = 0 level of H-2(+)((2)Sigma(+)(g)) molecule and are compared with previous theoretical calculations. Finally, we have calculated temperature-dependent rate constants using our presently evaluated cross sections and compared their average with the experimentally measured one.

Automated summary

This study analyzed the dynamics of the H + H-2(+) reaction from the electronically first excited state using diabatic potential energy surfaces constructed by employing the Beyond Born-Oppenheimer theory. The research extensively investigated charge transfer processes, calculated state-to-state probabilities, and compared temperature-dependent rate constants with experimental measurements.