Intersystem Crossing in the 1nπ* and 1ππ* States
Intersystem Crossing in the 1nπ* and 1ππ* States
复制标题
DOI：
10.1021/jp111892y
复制
发表时间：
2011-09-01
影响因子：
2.9
通讯作者：
Baba, Masaaki
中科院分区：
文献类型：
--
作者：
Baba, Masaaki
在N -杂环芳烃和羰基化合物的S - 1（1）nπ*态中观察到快速系间窜越。这归因于在相同能量区域与（3）ππ*态的自旋 - 轨道耦合。高分辨率光谱中转动谱线的大塞曼分裂证实了强烈的单重态 - 三重态混合。对于芳烃的S - 1（1）ππ*态，观察到的塞曼分裂相当小，并且系间窜越被认为是次要的。这些事实符合埃尔 - 赛义德规则，该规则指出（1）ππ*和（3）ππ*态之间的自旋 - 轨道耦合是禁阻的。还观察了几种衍生物的塞曼分裂，并讨论了取代对系间窜越速率的影响。
Fast intersystem crossing is observed in the S-1 (1)n pi* state of N-heterocyclic aromatic hydrocarbons and carbonyl compounds. It is attributed to spin-orbit coupling with the (3)pi pi* state in the same energy region. The strong singlet-triplet mixing was confirmed by large Zeeman splitting of rotational lines in a high-resolution spectrum. For the S-1 (1)pi pi* state of aromatic hydrocarbons, the observed Zeeman splitting was found to be considerably small, and intersystem crossing was considered to be minor. These facts are in accordance with El-Sayed's rude, which states spin-orbit coupling is forbidden between the (1)pi pi* and (3)pi pi* states. The Zeeman splitting of several derivatives was also observed and the substitution effect on the intersystem crossing rate is discussed.