Electronic relaxation of aniline in argon matrix: A site selective laser spectroscopy

International audienceAbsorption (S1←S0), fluorescence (S1→S0) and phosphorescence (T1→S0) spectra of aniline isolated in argon matrices are presented and analyzed. Upon selective laser excitation, two families of sites are characterized by electronic spectroscopy and excited state dynamics. A strong electron/phonon coupling is observed in the S1↔S0 transition due to a geometry change of the molecule. Phosphorescence spectra exhibit different vibronic intensity distribution for both sites; a1 in plane and b1 out-of-plane modes are observed. A direct estimation of the inversion splitting in the ground state (46 cm−1) is obtained from the presence of an intense doublet assigned to 3A1(0+)→1A1(0+,0−) vibronic transitions