| Autor: |
Jankowska J; Faculty of Chemistry, University of Warsaw, Pasteura 1, Warsaw 02-093, Poland. jjankowska@chem.uw.edu.pl., Sobolewski AL; Institute of Physics, Polish Academy of Sciences, al. Lotników 32/46, Warsaw 02-668, Poland. |
| Jazyk: |
angličtina |
| Zdroj: |
Physical chemistry chemical physics : PCCP [Phys Chem Chem Phys] 2024 Feb 07; Vol. 26 (6), pp. 5296-5302. Date of Electronic Publication: 2024 Feb 07. |
| DOI: |
10.1039/d3cp04148d |
| Abstrakt: |
Excited-state Proton-Coupled Electron Transfer (PCET) constitutes a key step in the photo-oxidation of small, electron-rich systems possessing acidic hydrogen atoms, such as water or alcohols, which can play a vital role in green hydrogen production. In this contribution, we employ ab initio quantum-chemical methods and on-the-fly nonadiabatic molecular dynamics simulations to study the mechanism and the photodynamics of PCET in 1 : 1 pyrido[2,3- b ]pyrazine complexes with methanol. We find the process to be ultrafast and efficient when the intramolecular hydrogen bond is formed with one of the β-positioned nitrogen atoms. The complex exhibiting a hydrogen bond with an isolated nitrogen site, on the contrary, shows much lower reactivity. We explain this effect with the stabilization of the reactive ππ* charge-transfer electronic state in the former case. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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