Wavepacket propagations for the early time dynamics of proton-coupled electron transfer in the charge-transfer state...

A charge-transfer (CT) excited state of NH₃Cl, generated by photo-detachment of an electron from the anionic NH₃Cl^- precursor, can be represented as H₂N⁺-H-Cl^- and proceeds to two chemical reactions: one reaction generating NH₂ and HCl resulting from a proton transfer (PT) and the other reaction producing NH₃ and a Cl atom resulting from an electron transfer (ET); both are coupled to form a typical proton-coupled electron transfer (PCET) process. The early time dynamics of this CT were studied using time-dependent wavepacket propagation on three nonadiabatically coupled electronic states in a reduced three-dimensional space. The electronic states were treated using the XMS-CASPT2/aug-cc-pVTZ ab initio methodology. The population dynamics of the three coupled electronic states were analyzed in detail to reveal the initial stage of the PCET process up to ∼100 fs, while the branching ratio, χ = PT/(ET+PT), was determined after wavepacket propagations of up to 2000 fs. Another main result is the dependence of χ on the vibration levels of the initial precursor anion and the isotope substitution of the connecting H atom with deuterium and tritium. Our study reveals the detailed microscopic features of the PCET process embedded in the CT state of the NH₃Cl complex and certain systematic dependences of the branching ratio χ on the above factors.