| Autor: |
Bensberg M; ETH Zürich, Laboratorium für Physikalische Chemie, Vladimir-Prelog-Weg 2, 8093 Zürich, Switzerland., Reiher M; ETH Zürich, Laboratorium für Physikalische Chemie, Vladimir-Prelog-Weg 2, 8093 Zürich, Switzerland. |
| Jazyk: |
angličtina |
| Zdroj: |
The journal of physical chemistry letters [J Phys Chem Lett] 2023 Mar 02; Vol. 14 (8), pp. 2112-2118. Date of Electronic Publication: 2023 Feb 20. |
| DOI: |
10.1021/acs.jpclett.2c03905 |
| Abstrakt: |
The accuracy of reaction energy profiles calculated with multiconfigurational electronic structure methods and corrected by multireference perturbation theory depends crucially on consistent active orbital spaces selected along the reaction path. However, it has been challenging to choose molecular orbitals that can be considered corresponding in different molecular structures. Here, we demonstrate how active orbital spaces can be selected consistently along reaction coordinates in a fully automatized way. The approach requires no structure interpolation between reactants and products. Instead, it emerges from a synergy of the Direct Orbital Selection orbital mapping ansatz combined with our fully automated active space selection algorithm autoCAS. We demonstrate our algorithm for the potential energy profile of the homolytic carbon-carbon bond dissociation and rotation around the double bond of 1-pentene in the electronic ground state. However, our algorithm also applies to electronically excited Born-Oppenheimer surfaces. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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