Mode-specific multi-channel dynamics of the F- + CHD2Cl reaction on a global ab initio potential energy surface
We report a detailed quasiclassical trajectory study for the dynamics of the ground-state and CH/CD stretching-excited F- + CHD2Cl(v(CH/CD) = 0,1) -> Cl- + CHD2F, HF + CD2Cl-, and DF + CHDCl- S(N)2, proton-, and deuteron-abstraction reactions using a full-dimensional global ab initio analytical p...
Elmentve itt :
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| Dokumentumtípus: | Cikk |
| Megjelent: |
2016
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| Sorozat: | JOURNAL OF CHEMICAL PHYSICS
145 No. 13 |
| doi: | 10.1063/1.4963664 |
| mtmt: | 3142888 |
| Online Access: | http://publicatio.bibl.u-szeged.hu/17923 |
| Tartalmi kivonat: | We report a detailed quasiclassical trajectory study for the dynamics of the ground-state and CH/CD stretching-excited F- + CHD2Cl(v(CH/CD) = 0,1) -> Cl- + CHD2F, HF + CD2Cl-, and DF + CHDCl- S(N)2, proton-, and deuteron-abstraction reactions using a full-dimensional global ab initio analytical potential energy surface. The simulations show that (a) CHD2Cl(v(CH/CD) = 1), especially for v(CH) = 1, maintains its mode-specific excited character prior to interaction, (b) the S(N)2 reaction is vibrationally mode-specific, (c) double inversion can occur and is enhanced upon CH/CD stretching excitations, (d) in the abstraction reactions the HF channel is preferred and the v(CH/CD) = 1 excitations significantly promote the HF/DF channels, (e) back-side rebound, back-side stripping, and front-side stripping are the dominant direct abstraction mechanisms based on correlated scattering-and attack-angle distributions, (f) the exact classical vibrational energy-based Gaussian binning (1GB) provides realistic mode-specific polyatomic product state distributions, (g) in the abstraction reactions CH and CD stretchings are not pure spectator modes and mainly ground-state products are produced, thus most of the initial energy transfers into product translation, and (h) the HF and DF product molecules are rotationally cold without any significant dependence on the reactant's and HF/DF vibrational states. Published by AIP Publishing. |
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| Terjedelem/Fizikai jellemzők: | Azonosító: 134303-Terjedelem: 16.o |
| ISSN: | 0021-9606 |