Automated reaction path searches for spin-forbidden reactions.

Many catalytic and biomolecular reactions containing transition metals involve changes in the electronic spin state. These processes are referred to as "spin-forbidden" reactions within nonrelativistic quantum mechanics framework. To understand detailed reaction mechanisms of spin-forbidden reactions, one must characterize reaction pathways on potential energy surfaces with different spin states and then identify crossing points. Here we propose a practical computational scheme, where only the lowest mixed-spin eigenstate obtained from the diagonalization of the spin-coupled Hamiltonian matrix is used in reaction path search calculations. We applied this method to the 6,4 FeO+  + H2 → 6,4 Fe+  + H2 O, 6,4 FeO+  + CH4 → 6,4 Fe+  + CH3 OH, and 7 Mn+  + OCS → 5 MnS+  + CO reactions, for which crossings between the different spin states are known to play essential roles in the overall reaction kinetics. © 2018 Wiley Periodicals, Inc.