Does the Cl + CH4 -> H + CH3Cl Reaction Proceed via Walden Inversion?
We report a chemically accurate global ab initio full-dimensional potential energy surface (PES) for the Cl(P-2(3/2)) + CH4 reaction improving the high-energy region of our previous PES [Czako, G.; Bowman, J. M. Science 2011, 334, 343-346]. Besides the abstraction (HCl + CH3) and the Walden-inversio...
Elmentve itt :
| Szerzők: | |
|---|---|
| Dokumentumtípus: | Cikk |
| Megjelent: |
2017
|
| Sorozat: | JOURNAL OF PHYSICAL CHEMISTRY A
121 No. 49 |
| doi: | 10.1021/acs.jpca.7b10226 |
| mtmt: | 3313323 |
| Online Access: | http://publicatio.bibl.u-szeged.hu/17919 |
| LEADER | 02249nab a2200217 i 4500 | ||
|---|---|---|---|
| 001 | publ17919 | ||
| 005 | 20200116090607.0 | ||
| 008 | 200116s2017 hu o 0|| zxx d | ||
| 022 | |a 1089-5639 | ||
| 024 | 7 | |a 10.1021/acs.jpca.7b10226 |2 doi | |
| 024 | 7 | |a 3313323 |2 mtmt | |
| 040 | |a SZTE Publicatio Repozitórium |b hun | ||
| 041 | |a zxx | ||
| 100 | 1 | |a Krotos László | |
| 245 | 1 | 0 | |a Does the Cl + CH4 -> H + CH3Cl Reaction Proceed via Walden Inversion? |h [elektronikus dokumentum] / |c Krotos László |
| 260 | |c 2017 | ||
| 300 | |a 9415-9420 | ||
| 490 | 0 | |a JOURNAL OF PHYSICAL CHEMISTRY A |v 121 No. 49 | |
| 520 | 3 | |a We report a chemically accurate global ab initio full-dimensional potential energy surface (PES) for the Cl(P-2(3/2)) + CH4 reaction improving the high-energy region of our previous PES [Czako, G.; Bowman, J. M. Science 2011, 334, 343-346]. Besides the abstraction (HCl + CH3) and the Walden-inversion substitution (H + CH3Cl) channels, the new PES accurately describes novel substitution pathways via retention of configuration. Quasiclassical trajectory simulation on this PES reveals that the substitution channel opens around 40 kcal/mol collision energy via Walden inversion and the retention cross sections raise from similar to 50 kcal/mol. At collision energy of 80 kcal/mol, the retention pathways provide nearly 40% of the substitution cross section, and retention substitution may become the dominant mechanism of the Cl + CH4 reaction at superhigh collision energies. The substitution probability can be as high as similar to 70% at zero impact parameter (b) and decreases rapidly with increasing b, whereas the abstraction opacity function is broad having 5-10% probability over a larger b-range. The high-energy angular distributions show scattering into forward and backward directions for the abstraction (direct stripping) and face-attack Walden-inversion substitution (direct rebound) channels, respectively. Retention can proceed via edge- and vertex-attack pathways producing dominant sideways scattering because the breaking C-H or Cl-H bond is usually at a side position of the forming Cl-C bond. | |
| 700 | 0 | 1 | |a Czakó Gábor |e aut |
| 856 | 4 | 0 | |u http://publicatio.bibl.u-szeged.hu/17919/1/JPCA_121_9415_2017.pdf |z Dokumentum-elérés |