Dynamics of vibrationally mediated photodissociation of CH₃CFCl₂

The vibrationally mediated photodissociation (VMP) of CH₃CFCl₂ with different quanta of C-H methyl stretches was studied. The time-of-arrival profiles of Cl photofragments were measured using the resonantly enhanced multiphoton ionization in a time-of-flight mass spectrometry (REMPI-TOF). The data analysis yielded the photofragment energy distributions and the recoil anisotropy parameters. The additional methyl group influenced the mechanism of the decay and the purely energetic effects due to the increased total energy became negligible. The modified wave function of the electronic ground state resulted in accessing differenr parts of the upper potential energy surfaces (PES) in a basically constant energy range.