D. Srinivas, H. Upadhyaya
Jun 15, 2016
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Journal
Chemical Physics
Abstract
Abstract The photodissociation dynamics of halogen substituted pyridines, namely, 3-chloropyridine (ClPy) and 3-chloro-2,4,5,6-tetrafluoropyridine (ClFPy), has been studied around 235 nm by detecting chlorine atoms in their spin orbit states Cl( 2 P 3/2 ) and Cl ∗ ( 2 P 1/2 ) using the REMPI-TOF technique. We have determined the translational energy distribution, the recoil anisotropy parameter, β , and the spin–orbit branching ratio, for chlorine atom elimination channels. The TOF profiles for Cl and Cl ∗ are found to be independent of laser polarization suggesting a zero value for β , within the experimental uncertainties. For 3-chloropyridine, the average translational energies for Cl and Cl ∗ elimination channels are determined to be 3.7 ± 1.0 and 7.0 ± 1.5 kcal/mol, respectively. Similarly, for 3-chloro-2,4,5,6-tetrafluoropyridine, the average translational energies for Cl and Cl ∗ elimination channels are determined to be 8.0 ± 1.5 and 9.0 ± 1.5 kcal/mol, respectively. The theoretical calculation suggests that the fluorine substitution increases the possibility of cross over to the π – σ ∗ state from the initially prepared π – π ∗ state.