HCl elimination in the photolysis of chlorobenzene at 266 nm: An FT-IR spectroscopy and quantum chemical study

Behera, B and Das, P (2021) HCl elimination in the photolysis of chlorobenzene at 266 nm: An FT-IR spectroscopy and quantum chemical study. In: Chemical Physics Letters, 774 .

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Abstract

The photolysis of chlorobenzene (C6H5Cl) in the gas phase has been studied at 266 nm using repetitive scan FT-IR spectroscopy and density functional theory (DFT) to understand the degradation mechanism relevant to combustion and atmospheric chemistry. Following 266 nm photolysis of C6H5Cl, ro-vibrational lines were observed in the region 3060�2625 cm�1, at 3317.8/ 3262.7 cm�1 and 1346.2/1301.2 cm�1, and at 3341.2 and 1232.7 cm�1. These infrared features are assigned to the hydrochloric acid (HCl), acetylene (C2H2), and 1,3-butadiyne (C4H2), respectively. Identification of C2H2 and C4H2 but not expected HCl co-product ortho-benzyne (o-C6H4) indicates, possibly, o-C6H4 further degraded into C2H2 + C4H2. B3PW91/aug-cc-pVTZ and CBS-QB3 calculated potential energy surfaces for the possible degradation channels of C6H5Cl shows that HCl elimination and C�Cl bond fission are major degradation paths. Their experimental branching ratio was determined to be 1:1. The RRKM rate of HCl elimination of C6H5Cl at 266 nm was found to be 3.8 � 102 s�1 and compared with the HF elimination rate in C6H5F. The possible degradation mechanism is discussed. © 2021 Elsevier B.V.

Item Type:	Journal Article
Publication:	Chemical Physics Letters
Publisher:	Elsevier B.V.
Additional Information:	The copyright for this article belongs to Elsevier B.V.
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	11 Aug 2021 10:45
Last Modified:	11 Aug 2021 10:45
URI:	http://eprints.iisc.ac.in/id/eprint/69089

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