Resonance Raman spectra were acquired for thiophene in cyclohexane solution with 239.5 and 266 nm excitation wavelengths that were in resonance with ϳ240 nm first intense absorption band. The spectra indicate that the Franck-Condon region photodissociation dynamics have multidimensional character with motion mostly along the reaction coordinates of six totally symmetry modes and three nontotally symmetry modes. The appearance of the nontotally symmetry modes, the C u S antisymmetry stretch +C u

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... C v C bend mode 21 ͑B 2 ͒ at 754 cm −1 and the H 7 C 3 u C 4 H 8 twist 9 ͑A 2 ͒ at 906 cm −1 , suggests the existence of two different types of vibronic-couplings or curve-crossings among the excited states in the Franck-Condon region. The electronic transition energies, the excited state structures, and the conical intersection points potential energy surfaces of thiophene were determined by using complete active space self-consistent field theory computations. These computational results were correlated with the Franck-Condon region structural dynamics of thiophene. The ring opening photodissociation reaction pathway through cleavage of one of the C u S bonds and via the conical intersection point 1 B 1 / 1 A 1 was revealed to be the predominant ultrafast reaction channel for thiophene in the lowest singlet excited state potential energy hypersurface, while the internal conversion pathway via the conical intersection point 1 B 2 / 1 A 1 was found to be the minor decay channel in the lowest singlet excited state potential energy hypersurface.