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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
Author(s) -
Nakatomi Taiki,
Koido Shoichi,
Watabe Yuya,
Takayanagi Toshiyuki
Publication year - 2019
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.25908
Subject(s) - atomic physics , spin states , chemistry , hamiltonian (control theory) , spin (aerodynamics) , physics , transition metal , mathematical optimization , biochemistry , mathematics , thermodynamics , catalysis
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.