Intersystem Crossing in the ¹nπ* and ¹ππ* States

Fast intersystem crossing is observed in the S(1)(1)nπ* state of N-heterocyclic aromatic hydrocarbons and carbonyl compounds. It is attributed to spin-orbit coupling with the (3)ππ* 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)ππ* 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 rule, which states spin-orbit coupling is forbidden between the (1)ππ* and (3)ππ* states. The Zeeman splitting of several derivatives was also observed and the substitution effect on the intersystem crossing rate is discussed.