Ultraviolet photodissociation dynamics of the n-butyl, s-butyl, and t-butyl radicals.

Abstract

Photodissociation dynamics of the jet-cooled n-butyl radical via the 3s Rydberg state and the s-butyl radical via the 3p Rydberg states in the ultraviolet region of 233 nm-258 nm, as well as the t-butyl radical via the 3d Rydberg states at 226 nm-244 nm, are studied using the high-n Rydberg atom time-of-flight technique. The H-atom photofragment yield spectra of the n-butyl, s-butyl, and t-butyl radicals show a broad feature centered around 247 nm, 244 nm, and 234 nm, respectively. The translational energy distributions of the H + C4H8 products, P(ET)'s, of the three radicals are bimodal, with a slow (low ET) component peaking at ∼6 kcal/mol and a fast (high ET) component peaking at ∼52 kcal/mol-57 kcal/mol, ∼43 kcal/mol, and ∼37 kcal/mol for n-butyl, s-butyl, and t-butyl, respectively. The fraction of the products' translational energy in the available energy, ⟨ fT⟩, is 0.31, 0.30, and 0.27 for n-butyl, s-butyl, and t-butyl, respectively. The H-atom product angular distributions of the slow component are isotropic for all three radicals, while those of the fast component are anisotropic for n-butyl and s-butyl with an anisotropy parameter β ∼ 0.7 and ∼ 0.3 and that of the fast component of t-butyl is nearly isotropic. The bimodal product translational energy and angular distributions indicate two dissociation pathways to the H + C4H8 products in these three radicals, a direct, prompt dissociation on the repulsive potential energy surface coupling with the Rydberg excited states, and a unimolecular dissociation of the hot radical on the ground electronic state after internal conversion from the Rydberg states.