Detection of ClCO with time-resolved Fourier-transform infrared absorptionspectroscopy

ClCO was produced as a reaction intermediate after irradiation of a flowing mixture of Cl-2/CO/Ar at 355 nm. A step-scan time-resolved Fourier-transfo rm infrared spectrometer operated in absorption mode was employed to detect ClCO. A transient spectrum at a resolution of 0.13 cm(-1) partially reveal s rotational structure with the Q-branch peaked at 1884.59 cm(-1); the tran sition is associated with the C-O stretching (nu (l)) mode of ClCO. Calcula tions with densityfunctional theory (B3LYP/aug-cc-pVTZ) predict the geometr y, vibrational and rotational parameters of (ClCO)-Cl-35 and (ClCO)-Cl-37. A simulated absorption spectrum based on these parameters agrees satisfacto rily with experimental observation. (C) 2001 Elsevier Science B.V. All righ ts reserved.