Photodissociation of gaseous acetyl chloride at 248 nm by time-resolved Fourier-transform infrared spectroscopy: the HCl, CO, and CH2 product channels.
In one-photon dissociation of gaseous acetyl chloride at 248 nm, time-resolved Fourier-transform infrared emission spectroscopy is used to detect the fragments of HCl, CO, and CH(2) in the presence of Ar or O(2). The high-resolution spectra of HCl and CO are analyzed to yield the corresponding internal energy deposition of 8.9 +/- 1.1 and 6.2 +/- 0.9 kcal/mol. The presence of the CH(2) fragment is verified by detecting the CO(2) product resulting from the reaction of CH(2) and the added O(2). The probability of the HCl formation via a hot Cl reaction with the precursor is examined to be negligible by performing two experiments, the CH(3)COCl pressure dependence and the measurement of Br(2) with Cl reaction. The HCl elimination channel under the Ar addition is verified to be slowed by 2 orders of magnitude, as compared to the Cl elimination channel. The observed fragments are proposed to dissociate on the hot ground electronic state via collision-induced internal conversion. A two-body dissociation channel is favored leading to HCl and CH(2)CO, followed by secondary dissociation.
Liu
Yu-Ting
YT
Department of Chemistry, National Taiwan University, Taipei 106, Taiwan.
Tsai
Ming-Tsang
MT
Liu
Chia-Yun
CY
Tsai
Po-Yu
PY
Lin
King-Chuen
KC
Shih
Y H
YH
Chang
A H H
AH
D000085:Acetates / Q000737:chemistry*; D001128:Argon / Q000737:chemistry; D002248:Carbon Monoxide / Q000737:chemistry*; D002712:Chlorides / Q000737:chemistry*; D005740:Gases / Q000737:chemistry; D006851:Hydrochloric Acid / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry; D010777:Photochemistry; D012399:Rotation; D017550:Spectroscopy, Fourier Transform Infrared; D013997:Time Factors; D014732:Vibration
D000085:Acetates; D002712:Chlorides; D005740:Gases; D001128:Argon; D002248:Carbon Monoxide; C081124:acetyl chloride; D006851:Hydrochloric Acid; D010100:Oxygen