Photodissociation of CH2BrCHBrC(O)Cl at 248 nm: probing Br2 as the primary fragment using cavity ring-down spectroscopy.

The photodissociation of 2,3-dibromopropionyl chloride (CH2BrCHBrC(O)Cl, 2,3-DBPC) at 248 nm was carried out to study Br2 as the primary molecular product in the B3Π+0u ← X1Σ+g transition using cavity ring-down absorption spectroscopy. The rotational spectra (v'' = 0-2) were acquired and assigned with the aid of spectral simulation. It is verified that the obtained Br2 fragment is attributed to the one-photon dissociation of 2,3-DBPC and is free from contributions of secondary reactions. The vibrational ratio of the Br2 population of v(0):v(1):v(2) is equal to 1:(0.58 ± 0.12):(0.23 ± 0.09), corresponding to the Boltzmann vibrational temperature of 623 ± 38 K. The quantum yield of Br2 eliminated from 2,3-DBPC is estimated to be 0.09 ± 0.04. The dissociation pathways of 2,3-DBPC and its potential energy surfaces were calculated using density functional theory. By employing the CCSD(T)//M062X/6-31+g(d,p) level of theory, transition state barriers and corresponding reaction energies were calculated for the Br, Cl, Br2, BrCl, HBr and HCl elimination channels. The unimolecular rate constant for Br2 elimination was determined to be 2.09 × 105 s-1 using Rice-Ramsperger-Kassel-Marcus (RRKM) theory, thus explaining the small quantum yield of the Br2 channel.

Cavity Ring-Down Absorption Spectroscopy: Optical Characterization of ICl Product in Photodissociation of CH2ICl at 248 nm.

Iodine monochloride (ICl) elimination from one-photon dissociation of CH2ICl at 248 nm is monitored by cavity ring-down absorption spectroscopy (CRDS). The spectrum of ICl is acquired in the transition of B3Π0 ← X1Σ+ and is confirmed to result from a primary photodissociation, that is, CH2ICl + hν → CH2 + ICl. The vibrational population ratio is determined with the aid of spectral simulation to be 1:(0.36 ± 0.10):(0.11 ± 0.05) for the vibrational levels ν = 0, 1, and 2 in the ground electronic state, corresponding to a Boltzmann-like vibrational temperature of 535 ± 69 K. The quantum yield of the ICl molecular channel for the reaction is obtained to be 0.052 ± 0.026 using a relative method in which the scheme CH2Br2 → CH2 + Br2 is adopted as the reference reaction. The ICl product contributed by the secondary collisions is minimized such that its quantum yield obtained is not overestimated. With the aid of the CCSD(T)//B3LYP/MIDI! level of theory, the ICl elimination from CH2ICl is evaluated to follow three pathways via either (1) a three-center transition state or (2) two isomerization transition states. However, the three-center concerted mechanism is verified to be unfavorable.