Benchmark ab Initio Characterization of the Complex Potential Energy Surface of the F- + CH3CH2CI Reaction
We compute benchmark structures, frequencies, and relative energies for the stationary points of the potential energy surface of the F-+ CH3CH2CI reaction using explicitly correlated ab initio levels of theory. CCSD(T)-F12b geometries and harmonic vibrational frequencies are obtained with the aug-cc...
Elmentve itt :
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| Dokumentumtípus: | Cikk |
| Megjelent: |
2017
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| Sorozat: | JOURNAL OF PHYSICAL CHEMISTRY A
121 No. 14 |
| doi: | 10.1021/acs.jpca.7b01572 |
| mtmt: | 3221113 |
| Online Access: | http://publicatio.bibl.u-szeged.hu/17916 |
| Tartalmi kivonat: | We compute benchmark structures, frequencies, and relative energies for the stationary points of the potential energy surface of the F-+ CH3CH2CI reaction using explicitly correlated ab initio levels of theory. CCSD(T)-F12b geometries and harmonic vibrational frequencies are obtained with the aug-cc-pVTZ and aug-cc-pVDZ basis sets, respectively. The benchmark relative energies are determined using a high-level composite method based on CCSD(T)-F12b/aug-cc-pVQZ frozen-core energies, CCSD(T)-F12b/cc-pCVTZ-F12 core electron correlation effects, and CCSD(T)F12b/aug-cc-pVDZ zero-point energy corrections. The S(N)2 channel leading to Cl-+ CH3CH2F (-33.2) can proceed via back-side (-11.5), front-side (29.1), and double inversion (18.0) transition states, whereas the bimolecular elimination (E2) products, Cl-+ HF + C2H4 (-19.3), can be formed via anti (-15.0) and syn (-7.3) saddle points, whose best adiabatic energies relative to F-+ CH3CH2CI are shown in parentheses in kcal/mol. Besides the SN2 and E2 channels, the 0 K reaction enthalpies of the HF + H3C-CHCl-(29.4), HT + H3C-CHClF (46.2), H-+ FH2C-CH2Cl (51.1), and FCl-+ CH3CH2 (49.7) product channels are determined. Utilizing the new benchmark data, the performance of the DF-MP2, MP2, MP2-F12, CCSD(T), and CCSD(T)-F12b methods with aug-cc-pVDZ and aug-cc-pVTZ basis sets is tested. |
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| Terjedelem/Fizikai jellemzők: | 2847-2854 |
| ISSN: | 1089-5639 |