Title

Spectroscopic and Computational Studies of Matrix-Isolated iso-CXBr3 (X=F,Cl,Br): Structure, Properties, and Photochemistry of Substituted Iso-Tribromomethanes

Document Type

Article

Publication Date

10-10-2012

Source Publication

Journal of Molecular Structure

Abstract

Iso-polyhalomethanes are important reactive intermediates in the condensed and gas-phase chemistry of halomethanes. Building upon our recent study of iso-bromoform, in this work the substituted iso-tribromomethanes (iso-CXBr3; X = F, Cl, Br) were characterized by matrix isolation infrared and UV/Vis spectroscopy, supported by ab initio calculations, to further probe the structure, spectroscopy, properties, and photochemistry of these important intermediates. Selected wavelength laser irradiation of CXBr3 samples in an inert rare gas (typically Ar; mixing ratio 1:500) held at ∼5 K yielded iso-CXBr3 (XBrC–Br–Br or Br2C–Br–X). The observed infrared and UV/Vis absorptions are in excellent agreement with computational predictions, and the energies of various stationary points on the CXBr3 Potential Energy Surfaces (PESs) were characterized computationally using DFT, MP2, and CCSD (T) methods in combination with triple-zeta quality basis sets. These calculations show that the isomers are minima on the PESs that lie ∼200 kJ/mol above the global CXBr3 minimum, yet are bound by some 50–70 kJ/mol in the gas-phase with respect to the CXBr2 + Br asymptote. Laser irradiation of the isomers resulted in back photoisomerization to CXBr3, and intrinsic reaction coordinate (IRC) calculations confirmed the existence of a first order saddle point connecting the two isomers. Calculations of important stationary points on the CXBr3 PESs show that in the gas-phase the isomerization barrier lies energetically near the threshold for simple bond fission. The iso-CXBr3 species are significantly stabilized in the condensed phase, due to the high degree of ion-pair character, as revealed by Natural Resonance Theory analysis.

Comments

Journal of Molecular Structure, Vol. 1025, (October 2012): 61–68. DOI: 10.1016/j.molstruc.2011.12.018.