The photodissociation dynamics of benzoyl chloride at 235 nm has been investigated and compared with that of 2-furoyl chloride. Atomic Cl and molecular HCl channels have been detected in benzoyl chloride by employing resonance-enhanced multiphoton ionization technique and time-of-flight mass spectrometry. Both the Cl fragments, Cl(²P_J=3/2, relative quantum yield 0.70 ± 0.15)
and Cl*(²P_J=1/2), show isotropic angular distribution and bimodal translational energy distributions. The predominant high kinetic energy channel contributes 72% to the C−Cl bond scission and arises from the S₁ state having nπ* character of benzoyl chloride. However, the low-energy Cl and HCl channels originate from the ground electronic state. The most plausible mechanism of HCl formation is proposed based on molecular orbital calculations. In contrast to benzoyl chloride, the HCl channel is not observed in 2-furoyl chloride on excitation at 235 nm, and this is attributed to an energy constraint