Infrared absorption of gaseous benzoylperoxy radical C(6)H(5)C(O)OO recorded with a step-scan Fourier-transform spectrometer

Abstract

A step-scan Fourier-transform infrared spectrometer coupled with a multipass absorption cell was utilized to monitor the transient species produced in gaseous reactions of benzoyl radical, C(6)H(5)CO, with O(2). C(6)H(5)CO was produced either from photolysis of acetophenone, C(6)H(5)C(O)CH(3), at 248 nm, or from photolysis of a mixture of benzaldehyde, C(6)H(5)CHO, and Cl(2) at 355 nm. Two intense bands near 1830 and 1226 cm(-1) are assigned to the C=O stretching (nu(6)) and the C-C stretching mixed with C-H deformation (nu(13)) modes, and two weaker bands near 1187 and 1108 cm(-1) are assigned to the nu(14) (C-H deformation) and nu(16) (O-O stretching/C-H deformation) modes of C(6)H(5)C(O)OO, the benzoylperoxy radical. These observed vibrational wave numbers and relative infrared intensities agree with those reported for syn-C(6)H(5)C(O)OO isolated in solid Ar and values predicted for syn-C(6)H(5)C(O)OO with the B3LYP/cc-pVTZ method. The simulated rotational contours of the two intense bands based on rotational parameters predicted with the B3LYP/cc-pVTZ method fit satisfactorily with experimental results. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3664304]