Investigating the Phase-Dependent Reactivity of Chlorine Dioxide Using Resonance Raman Spectroscopy

Abstract

Recent progress in understanding the phase-dependent reactivity of chlorine dioxide (OClO) is outlined. Specifically, resonance Raman intensity analysis (RRIA) and time-resolved resonance Raman (TRRR) studies of OClO photochemistry in solution are presented. The RRIA studies demonstrate that the optically prepared excited-state undergoes significant modification in solution relative to the gas phase. Specifically, the substantial evolution that occurs along the asymmetric-stretch coordinate in the gas phase is restricted in solution. The absence of substantial evolution along the asymmetric-stretch coordinate results in the preservation of ground-state symmetry in the excited state. The role of symmetry in defining the reaction coordinate and the solvent−solute interactions responsible for modification of the excited-state potential energy surface are discussed. TRRR studies performed with pump and probe wavelengths at 390 nm are presented which demonstrate that geminate recombination of the primary photo...