Spin‐inversion mechanisms in the reactions of transition metal cations (Sc+, Ti+, V+, Cr+, Mn+, Fe+, Co+, Ni+, and Cu+) with OCS in the gas phase: A perspective from automated reaction path search calculations. Issue 11 (29th January 2019) - Nakatomi, Taiki
Abstract: The mechanisms including spin‐inversion have been systematically studied for the M + + OCS → MS + + CO/MO + + CS (M denotes a transition metal from Sc to Cu) ion‐molecule reactions using the automated reaction path search method. We used the lowest mixed‐spin potential energy surface obtained from the diagonalization of the spin‐coupled Hamiltonian matrix, whose diagonal elements are taken to be the lowest two spin states. This scheme can effectively locate approximate minimum energy crossing points between the two potential energy surfaces with different spin multiplicities. The spin‐orbit couplings at spin‐inversion points have been calculated to understand the efficiencies of nonadiabatic transitions. The obtained reaction pathways and the calculated spin‐orbit couplings are employed to interpret previous experimental studies. Abstract : Spin‐inversion mechanisms have been systematically studied for a series of M + + OCS → MS + + CO reactions (M denotes a transition metal atom from Sc to Cu), using the spin‐coupled effective Hamiltonian approach combined with the automated reaction path search method. The obtained reaction pathways and the spin‐orbit couplings calculated at the spin‐inversion points are employed to interpret previous experimental measurements.