Benchmark Ab Initio Characterization of the Abstraction and Substitution Pathways of the Cl + CH3CN Reaction
We investigate the reaction pathways of the Cl + CH3CN system: hydrogen abstraction, methyl substitution, hydrogen substitution, and cyanide substitution, leading to HCl + CH2CN, ClCN/CNCl + CH3, ClCH2CN + H, and CH3Cl + CN, respectively. Hydrogen abstraction is exothermic and has a low barrier, whe...
Elmentve itt :
| Szerzők: | |
|---|---|
| Dokumentumtípus: | Cikk |
| Megjelent: |
2022
|
| Sorozat: | JOURNAL OF PHYSICAL CHEMISTRY A
126 No. 18 |
| Tárgyszavak: | |
| doi: | 10.1021/acs.jpca.2c01376 |
| mtmt: | 32895238 |
| Online Access: | http://publicatio.bibl.u-szeged.hu/24762 |
| LEADER | 02069nab a2200241 i 4500 | ||
|---|---|---|---|
| 001 | publ24762 | ||
| 005 | 20220726125259.0 | ||
| 008 | 220726s2022 hu o 0|| Angol d | ||
| 022 | |a 1089-5639 | ||
| 024 | 7 | |a 10.1021/acs.jpca.2c01376 |2 doi | |
| 024 | 7 | |a 32895238 |2 mtmt | |
| 040 | |a SZTE Publicatio Repozitórium |b hun | ||
| 041 | |a Angol | ||
| 100 | 1 | |a Tóth Petra | |
| 245 | 1 | 0 | |a Benchmark Ab Initio Characterization of the Abstraction and Substitution Pathways of the Cl + CH3CN Reaction |h [elektronikus dokumentum] / |c Tóth Petra |
| 260 | |c 2022 | ||
| 300 | |a 2802-2810 | ||
| 490 | 0 | |a JOURNAL OF PHYSICAL CHEMISTRY A |v 126 No. 18 | |
| 520 | 3 | |a We investigate the reaction pathways of the Cl + CH3CN system: hydrogen abstraction, methyl substitution, hydrogen substitution, and cyanide substitution, leading to HCl + CH2CN, ClCN/CNCl + CH3, ClCH2CN + H, and CH3Cl + CN, respectively. Hydrogen abstraction is exothermic and has a low barrier, whereas the other channels are endothermic with high barriers. The latter two can proceed via a Walden inversion or front-side attack mechanism, and the front-side attack barriers are always higher. The C-side methyl substitution has a lower barrier and also a lower endothermicity than the N-side reaction. The computations utilize an accurate composite ab initio approach and the explicitly correlated CCSD(T)-F12b method. The benchmark classical and vibrationally adiabatic energies of the stationary points are determined with the most accurate CCSD(T)-F12b/aug-cc-pVQZ energies adding further contributions of the post-(T) and core correlation, scalar relativistic effects, spin-orbit coupling, and zero-point energy corrections. These contributions are found to be non-negligible to reach subchemical accuracy. © | |
| 650 | 4 | |a Fizikai kémia, polimertudomány, elektrokémia (szárazelemek, akkumulátorok, üzemanyagcellák, fémek korróziója, elektrolízis) | |
| 700 | 0 | 1 | |a Szűcs Tímea |e aut |
| 700 | 0 | 1 | |a Czakó Gábor |e aut |
| 856 | 4 | 0 | |u http://publicatio.bibl.u-szeged.hu/24762/1/JPCA_126_2802_2022.pdf |z Dokumentum-elérés |