Resonance Raman Intensity Analysis of ClNO₂ Dissolved in Methanol

Abstract

Halogens such as chlorine are converted from halides, including ClNO(2), to reactive radicals by UV solar radiation. These radicals can affect ozone production and destruction in the stratosphere. Recently, it became clear that halogen radicals can also play a significant role in the chemistry of the troposphere. The photochemistry of ClNO(2) has been the subject of several studies in the gas and solid state that demonstrated a clear phase-dependent reactivity. Here, we report our initial studies of nitryl chloride in solution. Resonance Raman (RR) spectra of ClNO(2) dissolved in methanol after excitation within the 1(1)A(1)-2(1)A(1) absorption band (D band) in the region 200-240 nm are presented. RR intensity along the NO symmetric stretch coordinate (v(1)) at 1291 cm(-1) is observed at all excitation wavelengths, whereas limited intensity corresponding to the transition of the N-Cl symmetric stretch (v(3)) was only observed at 199.8 nm, whereas no intensity corresponding to the O-N-O symmetric bend (v(2)) was observed. Depolarization ratios and absolute resonance Raman cross sections for v(1) were obtained at several excitation wavelengths spanning the D band. Depolarization ratios were found to deviate significantly from 1/3, consistent with more than a single dipole-allowed electronic transition contributing to the scattering. RR intensity analysis (RRIA) reveals that two closely spaced excited electronic states contribute to the scattering, which are dissociative along the Cl-N coordinate. In this study the role the solvent environment plays in ClNO(2) state energetics and excited structural evolution along fundamental coordinates is discussed.