CASCSF study on the photochemical transposition reactions of pyrazines.

Several reaction pathways for the photochemical transformations of methyl-substituted pyrazine in its first excited state 1(pi --> pi*) have been determined using the CASSCF (six-orbital/six-electron active space) and MP2-CAS methods with the 6-311G(d) basis set. Our model investigations suggest that conical intersections play a crucial role in the photoisomerization of pyrazines. Moreover, the present theoretical findings indicate that all of the photoisomerizations of pyrazines adopt the same reaction path as follows: pyrazine --> Franck-Condon region --> conical intersection --> pyrimidine. That is, although an excited-state pyrazine molecule can initiate a phototransposition process easily, this process can be completed on the ground-state potential energy surface after passage through a conical intersection where a fast, radiationless decay is possible. The existence of these nonadiabatic reaction pathways is consistent with the available experimental observations of the photochemistry and photophysics of pyrazine and its methyl derivatives. In the present work, we propose a simple p-pi orbital topology model, which can be used as a diagnostic tool to predict the location of the conical intersections, as well as the geometries of the phototransposition products of various heterocycles.