Full-dimensional automated potential energy surface development and dynamics for the OH + C 2 H 6 reaction
We develop a full-dimensional analytical potential energy surface (PES) for the OH + C 2 H 6 reaction using the Robosurfer program system, which automatically (1) selects geometries from quasi-classical trajectories, (2) performs ab initio computations using a coupled-cluster singles, doubles, and p...
Elmentve itt :
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| Dokumentumtípus: | Cikk |
| Megjelent: |
2022
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| Sorozat: | JOURNAL OF CHEMICAL PHYSICS
157 No. 7 |
| Tárgyszavak: | |
| doi: | 10.1063/5.0104889 |
| mtmt: | 33119360 |
| Online Access: | http://publicatio.bibl.u-szeged.hu/25725 |
| Tartalmi kivonat: | We develop a full-dimensional analytical potential energy surface (PES) for the OH + C 2 H 6 reaction using the Robosurfer program system, which automatically (1) selects geometries from quasi-classical trajectories, (2) performs ab initio computations using a coupled-cluster singles, doubles, and perturbative triples-F12/triple-zeta-quality composite method, (3) fits the energies utilizing the permutationally invariant monomial symmetrization approach, and (4) iteratively improves the PES via steps (1)–(3). Quasi-classical trajectory simulations on the new PES reveal that hydrogen abstraction leading to H 2 O + C 2 H 5 dominates in the collision energy range of 10–50 kcal/mol. The abstraction cross sections increase and the dominant mechanism shifts from rebound (small impact parameters and backward scattering) to stripping (larger impact parameters and forward scattering) with increasing collision energy as opacity functions and scattering angle distributions indicate. The abstraction reaction clearly favors side-on OH attack over O-side and the least-preferred H-side approach, whereas C 2 H 6 behaves like a spherical object with only slight C–C-perpendicular side-on preference. The collision energy efficiently flows into the relative translation of the products, whereas product internal energy distributions show only little collision energy dependence. H 2 O/C 2 H 5 vibrational distributions slightly/significantly violate zero-point energy and are nearly independent of collision energy, whereas the rotational distributions clearly blue-shift as the collision energy increases. |
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| Terjedelem/Fizikai jellemzők: | 9 |
| ISSN: | 0021-9606 |