Resonance enhanced multiphoton ionisation (REMPI) detection of Cl(2Pj) atom in the photodissociation of halogenated pyrimidines at 235 nm: role of triplet states

Abstract

ABSTRACTThe dynamics of chlorine atom (2Pj) formation in the photodissociation process of halogen substituted pyrimidines, namely, 2,4,6-trichloropyrimidine and 5-chloro-2,4,6-trifluoropyrimidine have been studied around 235 nm using Resonance Enhanced Multiphoton Ionisation Time-of-Flight Mass Spectrometry technique. For the chlorine atom dissociation channel, we have determined the translational energy distribution, the recoil anisotropy parameter, β, and the spin–orbit branching ratio. In both the molecules, the TOF profiles for Cl (2P3/2) and Cl* (2P1/2) are found to be independent of laser polarisation suggesting a zero value for β, within the experimental uncertainties. For 2,4,6-trichloropyrimidine, the average translational energies for Cl and Cl* elimination channels are determined to be 6.0 ± 1.2 and 7.0 ± 1.5 kcal/mol, respectively. Similarly, for 5-chloro-2,4,6-trifluoropyrimidine, the average translational energies for Cl and Cl* elimination channels are determined to be 6.5 ± 1.2 and 7.9 ± 1.6 kcal/mol, respectively. Computational calculations are performed to generate the potential energy curves along the dissociating C-Cl bond using equation of motion coupled cluster with single and double excitations (EOM-CCSD) method. Computational studies suggest the role of triplet states in the photodissociation process forming the Cl atom.