Photodissociation Dynamics of Diacetylene Rydberg States.

The state-selective photodissociation of diacetylene (C4H2) was studied in the wavelength range of 127.5-164.4 nm by high-resolution Rydberg H atom time-of-flight spectroscopy measurements. In the wavelength region, two Rydberg series nR and nR' were state-selectively excited using tunable vacuum-ultraviolet laser radiation. In all photolysis wavelengths, two decay channels with different dissociation dynamics were observed. In one channel, the characteristic and isotropic translational energy distributions with a peak around 1800 cm(-1) can be found, suggesting statistical dissociation through internal conversion (IC) from the Rydberg state to the ground state and then dissociation on the ground-state surface. In contrast to this, in the second channel, nonstatistical and anisotropic translational energy distributions were observed, possibly through IC to the excited repulsive state. The vibrational progressions of C4H (A(2)Π) products have also been observed and assigned to the CCC bend and C≡C stretch progressions in the second channel at 3R Rydberg states.