ManyHF-based full-dimensional potential energy surface development and quasi-classical dynamics for the Cl + CH3NH2 reaction
A full-dimensional spin–orbit (SO)-corrected potential energy surface (PES) is developed for the Cl + CH3NH2 multi-channel system. Using the new PES, a comprehensive reaction dynamics investigation is performed for the most reactive hydrogen-abstraction reactions forming HCl + CH2NH2/CH3NH. Hartree–...
Elmentve itt :
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| Dokumentumtípus: | Cikk |
| Megjelent: |
2023
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| Sorozat: | JOURNAL OF CHEMICAL PHYSICS
159 No. 13 |
| Tárgyszavak: | |
| doi: | 10.1063/5.0166680 |
| mtmt: | 34187268 |
| Online Access: | http://publicatio.bibl.u-szeged.hu/30782 |
| LEADER | 02684nab a2200229 i 4500 | ||
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| 024 | 7 | |a 10.1063/5.0166680 |2 doi | |
| 024 | 7 | |a 34187268 |2 mtmt | |
| 040 | |a SZTE Publicatio Repozitórium |b hun | ||
| 041 | |a eng | ||
| 100 | 1 | |a Szűcs Tímea | |
| 245 | 1 | 0 | |a ManyHF-based full-dimensional potential energy surface development and quasi-classical dynamics for the Cl + CH3NH2 reaction |h [elektronikus dokumentum] / |c Szűcs Tímea |
| 260 | |c 2023 | ||
| 300 | |a 11 | ||
| 490 | 0 | |a JOURNAL OF CHEMICAL PHYSICS |v 159 No. 13 | |
| 520 | 3 | |a A full-dimensional spin–orbit (SO)-corrected potential energy surface (PES) is developed for the Cl + CH3NH2 multi-channel system. Using the new PES, a comprehensive reaction dynamics investigation is performed for the most reactive hydrogen-abstraction reactions forming HCl + CH2NH2/CH3NH. Hartree–Fock (HF) convergence problems in the reactant region are handled by the ManyHF method, which finds the lowest-energy HF solution considering several different initial guess orbitals. The PES development is carried out with the Robosurfer program package, which iteratively improves the surface. Energy points are computed at the ManyHF-UCCSD(T)-F12a/cc-pVDZ-F12 level of theory combined with basis set (ManyHF-RMP2-F12/cc-pVTZ-F12 – ManyHF-RMP2-F12/cc-pVDZ-F12) and SO (MRCI+Q/aug-cc-pwCVDZ) corrections. Quasi-classical trajectory simulations show that the CH3-side hydrogen abstraction occurs more frequently in contrast to the NH2-side reaction. In both cases, the integral cross sections decrease with increasing collision energy (Ecoll). A reaction mechanism shifting from indirect to direct stripping can be observed from the opacity functions, scattering angle, and translation energy distributions as Ecoll increases. Initial attack angle distributions reveal that chlorine prefers to abstract hydrogen from the approached functional group. The collision-energy dependence of the product energy distributions shows that the initial translational energy mainly transfers to product recoil. The HCl vibrational and rotational energy values are comparable and nearly independent of collision energy, while the CH2NH2 and CH3NH co-products’ vibrational energy values are higher than the rotational energy values with more significant Ecoll dependence. The HCl(v = 0) rotational distributions are compared with experiment, setting the direction for future investigations. | |
| 650 | 4 | |a Kémiai tudományok | |
| 700 | 0 | 1 | |a Czakó Gábor |e aut |
| 856 | 4 | 0 | |u http://publicatio.bibl.u-szeged.hu/30782/3/34187268_megjelent.pdf |z Dokumentum-elérés |