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2128347 
Journal Article 
A Theoretical Study on Decomposition and Rearrangement Reaction Mechanism of Trichloroacetyl Chloride (CCl3COCl) 
Shankar, R; Kolandaivel, P; Senthilkumar, K 
2011 
Yes 
International Journal of Quantum Chemistry
ISSN: 0020-7608
EISSN: 1097-461X 
111 
14 
3482-3496 
WOS:000295366300004 
In the present study, the possible decomposition and rearrangement reaction profile of trichloroacetyl chloride have been studied using UMP2/6-311++G (2d, 2p) level of ab initio and UB3LYP/6-311++G (2d, 2p) level of density functional theory methods. The harmonic vibrational frequencies were calculated at the same level of theory used for the characterization of stationary points and zero-point vibrational energy corrections. The potential energy barrier and activation energy between each step of the reaction have been calculated for the seven possible reaction pathways (Ia-c, IIa-b, IIIa-b). The trichloroacetyl chloride is an asymmetric ketone where the two a bonds of acetyl chloride, the C-C and C-Cl bonds are strong with dissociation energy of 72 kcal/mol. The phosgene (COCl2), dichloroketene (CCl2CO), carbon dichloride (CCl2), carbon tetrachloride (CCl4), and carbon monoxide (CO) are the major dominant products on the decomposition of the trichloroacetyl chloride. These resultant products are more hazards than the parent trichloroacetyl chloride molecules. The positive value of the reaction energy indicate that the overall reaction profile is found to be endothermic at the UMP2 and UBLYP/6-311++G(2d, 2p) levels of theory, respectively, at UMP2/6-311G** optimized geometry. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 111: 3482-3496, 2011 
reaction mechanism; trichloroacetyl chloride; phospogene; carbon tetrachloride; dichloroketene; carbon monoxide