Photodissociation of cyanogen: Angle and velocity distributions of state resolved fragments

Abstract

The disposal of excess energy above the dissociation threshold into internal excitation and translation in a photochemical decomposition of C2N2 has been determined by utilizing a technique by which measurements of the recoil velocity distribution for particular rotational states are possible. Simple phase space theory calculations appear to give a fairly good interpretation of the rotational energy distributions in a particular vibrational state, while the vibrational energy disposal is definitely nonstatistical with only about 63% of the total population predicted by statistical calculation in the first vibrational state and no excitation observed in the v=2 state. Our experimental results support the previous predictions of high translational energy disposal ( fT=75%) compared to a low or moderate product internal state excitations ( fR=18.6%, fv=6.4%). We also measure the dissociation energy of C2N2 to be 133±1 kcal/mol rather than the previously reported 128±1 kcal/mol.