CHARACTERIZATION OF THE S-1-S-2 CONICAL INTERSECTION IN PYRAZINE USING AB-INITIO MULTICONFIGURATION SELF-CONSISTENT-FIELD AND MULTIREFERENCE CONFIGURATION-INTERACTION METHODS

Potential-energy surfaces of the three lowest singlet states of pyrazine have been calculated as a function of ab initio determined ground-state normal coordinates, using complete-active-space self-consistent-field (CASSCF) and multireference configuration interaction (MRCI) techniques. The conical intersection of the S-1 and S-2 adiabatic potential-energy surfaces has been mapped out in selected subspaces spanned by the most relevant vibrational coordinates. A unitary transformation from the adiabatic to a quasidiabatic electronic representation is performed, which eliminates the rapid variations of the wave functions responsible for the singularity of the nonadiabatic coupling element. Transition-dipole-moment functions have been obtained in the adiabatic and in the diabatic representation. The leading coefficients of the Taylor expansion of the diabatic potential-energy and transition-dipole-moment surfaces in terms of ground-state normal coordinates at the reference geometry have been obtained at the CASSCF/MRCI level. Using a vibronic-coupling model Hamiltonian based on this Taylor expansion, the absorption spectrum of the interacting S-1-S-2 manifold has been calculated, taking account of the four spectroscopically most relevant modes.