UV photodissociation dynamics of CHI2Cl and its role as a photolytic precursor for a chlorinated Criegee intermediate

Abstract

Photolysis of geminal diiodoalkanes in the presence of molecular oxygen has become an established route to the laboratory production of several Criegee intermediates, and such compounds also have marine sources. Here, we explore the role that the trihaloalkane, chlorodiiodomethane (CHI₂Cl), may play as a photolytic precursor for the chlorinated Criegee intermediate ClCHOO. CHI₂Cl has been synthesized and its UV absorption spectrum measured; relative to that of CH₂I₂ the spectrum is shifted to longer wavelength and the photolysis lifetime is calculated to be less than two minutes. The photodissociation dynamics have been investigated using DC slice imaging, probing ground state I and spin–orbit excited I* atoms with 2 + 1 REMPI and single-photon VUV ionization. Total translational energy distributions are bimodal for I atoms and unimodal for I*, with around 72% of the available energy partitioned in to the internal degrees of freedom of the CHICl radical product, independent of photolysis wavelength. A bond dissociation energy of D₀ = 1.73 ± 0.11 eV is inferred from the wavelength dependence of the translational energy release, which is slightly weaker than typical C–I bonds. Analysis of the photofragment angular distributions indicate dissociation is prompt and occurs primarily via transitions to states of A′′ symmetry. Complementary high-level MRCI calculations, including spin–orbit coupling, have been performed to characterize the excited states and confirm that states of A′′ symmetry with highly mixed singlet and triplet character are predominantly responsible for the absorption spectrum. Transient absorption spectroscopy has been used to measure the absorption spectrum of ClCHOO produced from the reaction of CHICl with O₂ over the range 345–440 nm. The absorption spectrum, tentatively assigned to the syn conformer, is at shorter wavelengths relative to that of CH₂OO and shows far weaker vibrational structure.