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Thermochemistry of Halomethanes CFnBr4–n (n = 0–3) Based on iPEPICO Experiments and Quantum Chemical Computations

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Paul Scherrer Institut, 5232 Villigen, Switzerland
Science Institute, University of Iceland, Dunhagi 3, 107 Reykjavík, Iceland
§ University of the Pacific, Stockton, California 95211, United States
Cite this: J. Phys. Chem. A 2011, 115, 46, 13443–13451
Publication Date (Web):October 10, 2011
https://doi.org/10.1021/jp208018r
Copyright © 2011 American Chemical Society

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    Abstract

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    Internal energy selected bromofluoromethane cations were prepared and their internal energy dependent fragmentation pathways were recorded by imaging photoelectron photoion coincidence spectroscopy (iPEPICO). The first dissociation reaction is bromine atom loss, which is followed by fluorine atom loss in CF3Br and CF2Br2 at higher energies. Accurate 0 K appearance energies have been obtained for these processes, which are complemented by ab initio isodesmic reaction energy calculations. A thermochemical network is set up to obtain updated heats of formation of the samples and their dissociative photoionization products. Several computational methods have been benchmarked against the well-known interhalogen heats of formation. As a corollary, we stumbled upon an assignment issue for the ClF heat of formation leading to a 5.7 kJ mol–1 error, resolved some time ago, but still lacking closure because of outdated compilations. Our CF3+ appearance energy from CF3Br confirms the measurements of Asher and Ruscic ( J. Chem. Phys. 1997, 106, 210) and Garcia et al. ( J. Phys. Chem. A 2001, 105, 8296) as opposed to the most recent result of Clay et al. ( J. Phys. Chem. A 2005, 109, 1541). The ionization energy of CF3 is determined to be 9.02–9.08 eV on the basis of a previous CF3–Br neutral bond energy and the CF3 heat of formation, respectively. We also show that the breakdown diagram of CFBr3+, a weakly bound parent ion, can be used to obtain the accurate adiabatic ionization energy of the neutral of 10.625 ± 0.010 eV. The updated 298 K enthalpies of formation ΔfHo(g) for CF3Br, CF2Br2, CFBr3, and CBr4 are reported to be −647.0 ± 3.5, −361.0 ± 7.4, −111.6 ± 7.7, and 113.7 ± 4 kJ mol–1, respectively.

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    Detailed computed energies for the benchmarking of computational methods as well as the thermochemical network data can be downloaded. This information is available free of charge via the Internet at http://pubs.acs.org.

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