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Automated reaction path searches for spin‐forbidden reactions
Author(s) -
Takayanagi Toshiyuki,
Nakatomi Taiki
Publication year - 2018
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.25202
Subject(s) - spin states , hamiltonian (control theory) , spin (aerodynamics) , eigenvalues and eigenvectors , transition state , hamiltonian matrix , chemistry , path (computing) , catalysis , physics , quantum mechanics , atomic physics , thermodynamics , symmetric matrix , mathematics , mathematical optimization , biochemistry , computer science , programming language
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 + + H 2 → 6,4 Fe + + H 2 O, 6,4 FeO + + CH 4 → 6,4 Fe + + CH 3 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.