title: Multichannel reaction of C2Cl3 + O2 studied by time-resolved Fourier transform infrared emission spectroscopy.
abstract: The multichannel reaction of the C(2)Cl(3) radical with O(2) has been studied thoroughly by step-scan time-resolved Fourier transform infrared emission spectroscopy. Vibrationally excited products of Cl(2)CO, CO, and CO(2) are observed and three major reaction channels forming respectively ClCO + Cl(2)CO, CO + CCl(3)O, and CO(2) + CCl(3) are identified. The vibrational state distribution of the product CO is derived from the spectral fitting, and the nascent average vibrational energy of CO is determined to be 59.9 kJ/mol. A surprisal analysis is applied to evaluate the vibrational energy disposal, which reveals that the experimentally measured CO vibrational energy is much more than that predicted by statistical model. Combining previous ab initio calculation results, the nonstatistical dynamics and mechanism are characterized to be barrierless addition-elimination via short-lived reaction intermediates including the peroxy intermediate C(2)Cl(3)OO* and a crucial three-member-ring COO intermediate.
authors: State Key Laboratory of Molecular Reaction Dynamics and Beijing National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, People's Republic of China.
authors: Tiancheng
authors: T
authors: Xiang
authors: Kunhui
authors: K
authors: Liu
authors: Shaolei
authors: S
authors: Zhao
authors: Hongmei
authors: H
authors: Su
authors: Fanao
authors: F
authors: Kong
authors: Baoshan
authors: B
authors: Wang