Kinetics and mechanism of 3-chloro-2-methyl-1-propene(3-ClMP) initiated by OH radical: an insight from DFT calculations[1]. (1st February 2019)

• Record Type: Journal Article
• Authors: Begum, Saheen Shehnaz; Gour, Nand Kishor; Baruah, Satyajit Dey; Deka, Ramesh Chandra
• Is Part Of: Molecular physics. Volume 117:Number 3(2019)
• Page Start: 280
• Page End: 288
• Publication Date: 2019-02-01
• Subjects: 3-ClMP -- CTST -- rate constant -- branching ratio -- lifetime; Molecules -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Molécules -- Périodiques; Chimie physique et théorique -- Périodiques; 539.6.05
• DOI: 10.1080/00268976.2018.1509146
• Languages: English
• ISSNs: 0026-8976

Abstract

ABSTRACT: In this manuscript, OH-initiated gas phase reactions of 3-chloro-2-methyl-1-propene [CH2 =C(CH3 )CH2 Cl] has been carried out by using density functional theory (DFT) method. We have chosen M06-2X hybrid density functional method along with 6-31 + G(d, p) basis set for optimisation and vibrational frequency calculations of all the relevant molecular species of the titled reaction. Energetic calculations have been further refined at CCSD(T) method along with cc-pVTZ basis set in order to obtain higher degree of precision of thermo-chemical and kinetic results. Energy profile is presented for all stationary points involved in the titled reaction and thermochemistry for all possible reaction channels (H-abstraction and OH-addition reactions) has been analysed. Canonical Transition State Theory (CTST) has been employed to determine the rate constants within the temperature range of 250–450 K and Our reported rate constant at 298 K are found to be close to the reported experimental rate constant. The atmospheric lifetime of the titled molecule has also been reported in this work. We have also reported standard enthalpies of formation of the titled molecule and generated product radicals by using group-balanced isodesmic reaction schemes. GRAPHICAL ABSTRACT: