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Abstract
Spin-orbit coupling plays an important role in determining the mechanisms and kinetics of spin-forbidden reactions and many reactions exhibiting two-state reactivity. Spin-orbit coupling can allow the system to change its spin state, especially when potential energy surfaces (PESs) of two spin states approach each other. Here, we introduce a convenient new approximation method for locating stationary points on the lowest mixed-spin potential energy surface along a reaction pathway by using density functional calculations. The mixing of different spin states is achieved by introducing the spin-orbit coupling into the electronic Hamiltonian using a pre-defined coupling constant. Two examples are given using the new methodology: (a) a CO association reaction with the coordinatively unsaturated Fe(CO)4 complex and (b) an α-H elimination reaction of a model complex containing W. We computed a Gibbs free energy of activation of 2.8 kcal mol-1 for the CO association reaction, which is reasonably consistent with the experimentally measured reaction rate. For the H elimination reaction, the spin change occurs at a relatively low energy, and the present treatment allows one conclude that kinetics of the reaction can be reasonably well described without spin-orbit coupling.
Original language | English (US) |
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Pages (from-to) | 4129-4136 |
Number of pages | 8 |
Journal | Physical Chemistry Chemical Physics |
Volume | 20 |
Issue number | 6 |
DOIs | |
State | Published - 2018 |
Bibliographical note
Publisher Copyright:© 2018 the Owner Societies.
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Dive into the research topics of 'Transition states of spin-forbidden reactions'. Together they form a unique fingerprint.Projects
- 1 Finished
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Energy Frontier Research Center For Inorganometallic Catalyst Design (DE-SC0012702)
Gagliardi, L. (PI), Cramer, C. (CoI), Lu, C. C. (CoI), Penn, L. (CoI), Stein, A. (CoI) & Truhlar, D. G. (CoI)
U.S. DEPARTMENT OF ENERGY (USDOE)
8/1/14 → 7/31/18
Project: Research project