High-Level-Optimized Stationary Points for the F-(H2O) + CH3I System Proposing a New Water-Induced Double-Inversion Pathway /
We report 29 stationary points for the F-(H2O) + CH3I reaction obtained by using the high-level explicitly correlated CCSD(T)-F12b method with the aug-cc-pVDZ basis set for the determination of the benchmark structures and frequencies and the aug-cc-pVQZ basis for energy computations. The stationary...
Elmentve itt :
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| Dokumentumtípus: | Cikk |
| Megjelent: |
2019
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| Sorozat: | JOURNAL OF PHYSICAL CHEMISTRY A
123 No. 2 |
| doi: | 10.1021/acs.jpca.8b10630 |
| mtmt: | 30436830 |
| Online Access: | http://publicatio.bibl.u-szeged.hu/17906 |
| Tartalmi kivonat: | We report 29 stationary points for the F-(H2O) + CH3I reaction obtained by using the high-level explicitly correlated CCSD(T)-F12b method with the aug-cc-pVDZ basis set for the determination of the benchmark structures and frequencies and the aug-cc-pVQZ basis for energy computations. The stationary points characterize the monohydrated F-- and OH--induced Walden-inversion pathways and, for the first time, the front-side attack and F--induced double-inversion mechanisms leading to CH3F with retention as well as the novel H2O-induced double inversion retention pathway producing CH3OH. Hydration effectively increases the relative energies of the stationary points, but the monohydrated inversion pathways are still barrierless, whereas the front-side attack and double-inversion barrier heights are around 30 and 20 kcal/mol, respectively. |
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| Terjedelem/Fizikai jellemzők: | 454-462 |
| ISSN: | 1089-5639 |