Electronic excitation spectrum of thiophene studied by symmetry-adapted cluster configuration interaction method

Electronic excitation spectrum of thiophene was investigated by the symmetry-adapted cluster (SAC)/SAC configuration interaction method. Seventy singlet and four lowest triplet electronic states of thiophene were computed to give a detailed satisfactory theoretical interpretation of the vacuum ultraviolet (VUV) spectrum and the electron energy loss spectrum of thiophene. The present calculations gave the 2 (1)A(1) valence state at 5.41 eV and the 1 B-1(2) valence state at 5.72 eV with oscillator strengths 0.0911 and 0.1131, respectively, and the 5 (1)A(1) valence state at 7.32 eV and the 4 B-1(2) valence state at 7.40 eV with oscillator strengths 0.3614 and 0.1204, respectively. These valence-excited states were assigned to the two strong absorption bands of the VUV spectrum centered around 5.5 and 7.05 eV, respectively. A number of Rydberg transitions were obtained and assigned to the 6.0, 6.6, and 7.5-8.7 eV, etc. energy regions. The similarities and differences in the electronic excitations between thiophene and other five-membered ring compounds were discussed. The accuracy and assignment of the present results are compared with those of the recent theoretical studies by CASPT2 and multireference double configuration interaction methods. (C) 2001 American Institute of Physics.