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研究组在质子转移领域的研究成果在Physical Chemistry Chemical Physics在线发表


2019-01-13

在蒋臣威副教授和Wolfgang Domcke教授的共同指导下,博士生庞晓娟同学为第一作者完成的关于“Photoinduced electron-driven proton transfer from water to an N-heterocyclic chromophore: nonadiabatic dynamics studies for pyridine-water clusters” 的研究工作最近在国际高水平学术期刊Physical Chemistry Chemical Physics在线发表。

 

论文摘要:

It has been found in recent molecular beam experiments that pyridine molecules photoexcited at 255 nm can abstract hydrogen atoms from hydrogen-bonded water molecules in pyridine-water clusters, resulting in pyridinyl-hydroxyl radical pairs. The reaction could only be detected for clusters containing at least four water molecules. To provide insight into the mechanisms of this reaction, we performed ab initio excited-state trajectory surface-hopping dynamics simulations for two pyridine-water complexes, containing one and four water molecules, respectively, using the second-order algebraic-diagrammatic-construction (ADC(2)) electronic-structure method. A surface-hopping algorithm based on the Landau-Zener formula has been used to evaluate the transition probability between electronic states. The formation of the pyridinyl radical via an electron-driven proton transfer (EDPT) process from water to pyridine is confirmed by the simulations. The analysis of the competing excited-state reaction mechanisms up to 500 fs reveals that adiabatic relaxation to local minima of the S1(nπ*) potential-energy surface is the dominant channel in both clusters, followed by internal conversion to the electronic ground state via so-called ring-puckering conical intersections. The efficiency of the latter contribution is weakly dependent of the size of the clusters. The EDPT reaction occurs on the fastest time scales (faster than 200 fs) with a branching ratio of several percent. It is found to be four times more efficient in the pyridine-(H2O)4 cluster than in the pyridine-H2O cluster, which is qualitatively consistent with the experimental observations. A detailed understanding of the photoinduced reaction mechanisms in complexes of N-heterocyclic chromophores with water molecules is of relevance for future systematic knowledge-based developments of optimized materials for photocatalytic water splitting with sunlight.

 

论文在线地址:https://pubs.rsc.org/en/content/articlelanding/2019/cp/c8cp07015f#!divAbstract

 

恭喜博士生庞晓娟!



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