Photo-oxidation of methanol in complexes with pyrido[2,3-b]pyrazine: a nonadiabatic molecular dynamics study.
Phys Chem Chem Phys
; 26(6): 5296-5302, 2024 Feb 07.
Article
em En
| MEDLINE
| ID: mdl-38265828
ABSTRACT
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 ß-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.
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MEDLINE
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En
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2024
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Article