期刊
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
卷 20, 期 6, 页码 4129-4136出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c7cp07227a
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资金
- Inorganometallic Catalysis Design Center, an Energy Frontier Research Center - U.S. Department of Energy, Office of Science, Basic Energy Sciences [DE-SC0012702]
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 alpha-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.
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