Infrared multiphoton chemistry of fluoroform-d

Abstract

The infrared multiphoton chemistry of CF3D has been investigated in the ν2 and ν5 bands. The primary dissociation step forms DF and CF2. The major sink for the biradical is dimerization to form C2F4; this process preserves the 13C/12C isotopic selectivity which is reasonably high (α ≈ 20). The isotopic selectivity for 2H/1H is impaired by some scrambling reaction involving excited substrate. The possible nature of this scrambling reaction is discussed. In comparison with other CF3X systems (X = I, Br, Cl), CF3D is difficult to decompose, having low dissociation probability, and appears to decompose only after collisional activation.