期刊
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
卷 105, 期 35, 页码 12707-12712出版社
NATL ACAD SCIENCES
DOI: 10.1073/pnas.0801062105
关键词
conical intersection; excited-state hydrogen transfer; nonadiabatic transition
资金
- Deutsche Forschungsgemeinschaft
- Munich Centre of Advanced Photonics
- Leibniz Rechenzentrum der Bayerischen Akademie der Wissenschaften
- Alexander von Humboldt Foundation
The photochemical dynamics of the pyrrole-pyridine hydrogen-bonded complex has been investigated with computational methods. In this system, a highly polar charge-transfer state of (1)pi pi* character drives the proton transfer from pyrrole to pyridine, leading to a conical intersection of S, and So energy surfaces. A two-sheeted potential-energy surface including 39 in-plane nuclear degrees of freedom has been constructed on the basis of ab initio multiconfiguration electronic-structure data. The non-Born-Oppenheimer nuclear dynamics has been treated with time-dependent quantum wave-packet methods, including the two or three most relevant nuclear degrees of freedom. The effect of the numerous weakly coupled vibrational modes has been taken into account with reduced-density-matrix methods (multilevel Redfield theory). The results provide insight into the mechanisms of excited-state deactivation of hydrogen-bonded aromatic systems via the election-driven proton-transfer process. This process is believed to be of relevance for the ultrafast excited-state deactivation of DNA base pairs and may contribute to the photostability of the molecular encoding of the genetic information.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据