Low-lying electronic states and their nonradiative deactivation of thieno[3,4-b]pyrazine: an ab initio study.

State-averaged complete active space self-consistent field (SA-CASSCF) calculations have been used to locate the four low-lying electronic states of thieno[3,4-b]pyrazine (TP), and their vertical excitation energies and emission energies have been determined by means of the multistate complete active space with second-order perturbation theory (MS-CASPT2) calculations. The present results indicate that the first weak (1)nπ∗ excited state has a C(s)-symmetry structure, unlike two bright (1)ππ∗ excited states in C(2v) symmetry. The predicted vertical excitation energies of the three low-lying excited states in the gas phase are 3.41, 3.92, and 4.13 eV at the restricted-spin coupled-cluster single-double plus perturbative triple excitation [RCCSD(T)] optimized geometry, respectively. On the basis of calculations, a new assignment to the observed spectra of TP was proposed, in which the (1)nπ∗ state should be responsible for the weak absorption centred at 3.54 eV and the two closely spaced (1)ππ∗ states account for the two adjacent absorption bands observed at 3.99 and 4.15 eV. The predicted vertical emission energies lend further support to our assignments. Surface hopping dynamics simulations performed at the SA-CASSCF level suggest that the plausible deactivation mechanism comprises an ultrafast relaxation of the (1)ππ∗ excited states to (1)nπ∗ excited state, followed by a slow conversion to the S(0) ground state via a conical intersection. This internal conversion is accessible, since the MS-CASPT2 predicted energy barrier is ∼0.55 eV, much lower than the Franck-Condon point populated initially under excitation. The dynamical simulations on the low-lying states for 500 fs reveal that the relatively high (1)ππ∗ excited states can be easily trapped in the (1)nπ∗ excited state, which will increase the lifetime of the excited thieno[3,4-b]pyrazine.