Quantum chemistry and density functional calculations of formyl chloride

Ab initio MRD-CI study of excited states of formyl chloride HClCO and photofragmentation along Cl–C cleavage

“…1. This equilibrium geometry is in reasonable agreement with both, prior experimental work of Davis and Gerry [47] as well as theoretically determined values [20,51]. The deviations of the bond lengths and bond angles are less than 0.01 Å and 0.2°respectively.…”

“…This is in reasonable agreement with the experimental value of 4.76 eV reported by both Libuda et al [18] and Judge and Moule [61]. QCISD(T) calculations of the vertical excitation energy of formyl chloride by Bent and co-workers [51] resulted in 4.81 eV, while the same authors obtained 4.71 eV with density functional calculations. It can be seen from Fig.…”

“…The equilibrium geometry of formyl chloride has been determined both experimentally [47][48][49] and theoretically [19][20][21][50][51][52]. However, as a starting point of our investigation of excited states of formyl chloride we fully optimised the geometry at the QCISD/6-311G(d,p) (quadratic configuration interaction with single-and double-excitations [53]) level of theory using the Gaussian 98 [54] program package.…”

Unimolecular Dissociation of Formyl Halides HXCO → CO + HX (X= F, Cl): An Ab Initio Direct Classical Trajectory Study

“…The mode specificity of the reactants, the reaction threshold, and the distribution of energy in the products are some of the details that are studied. In this respect, the photodissociation of formaldehyde (H 2 CO) has been studied extensively by experiment − and theory. − Formyl fluoride (HFCO) − and formyl chloride (HClCO) ,, have received much less attention. These fluorine- and chlorine-substituted analogues of H 2 CO are formed in the degradation of hydrochlorofluorocarbons (HCFC). , The photodissociation of these halogenated molecules is of importance, as their degradation has important consequences for the earth's protective ozone layer. − The various dissociation routes for HXCO are Of these pathways, the molecular dissociation channel (reaction 3) is found to be the lowest-energy path.…”

A High-Resolution Fourier Transform Infrared Study of the Out-of-Plane Bending Fundamentals of HCOCl and DCOCl

“…For example, degradation of proposed CFC alternatives of the type CF 3 CHXY (X, Y Å H, F, or Cl) leads to the formation of HXCO carbonyl compounds (1,2). Chloroethenes such as vinyl chloride and trichloroethene are released into the atmosphere in large quantities and are degraded by reactions with OH radicals to produce formyl chloride as a major product (3)(4)(5).…”