Abstract
To resolve discrepancies concerning the magnitude of the electron affinities of perfluoro cyclopropane and perfluorocyclobutane, quantum chemical calculations have been carried out with the MP2 and CCSD(T), methods in conjunction with augmented correlation consistent basis sets (aug-cc-pVX Z, X = D, T, Q). Though no experimental values have been found for perfluoro cyclopropane, we estimate its electron affinity to be 0.17 eV (0.00 eV without zero-point vibrational energy corrections). In addition, determination of the electron affinity of perfluorocyclobutane (0.61 and 0.44 eV with and without zero-point vibrational energy corrections, respectively) is in good agreement with experimental values reported by Miller and co-workers (0.63 ±0.05 eV). This study also demonstrates that the widely prescribed B3LYP/DZP++ model chemistry for computing electron affinities does not correctly describe these systems. © 2006 American Chemical Society.
Recommended Citation
A. M. Elsohly et al., "Reliable Electron Affinities of Perfluorocyclopropane and Perfluorocyclobutane from Convergent Ab Initio Computations," Journal of Physical Chemistry A, vol. 110, no. 5, pp. 1975 - 1977, American Chemical Society, Feb 2006.
The definitive version is available at https://doi.org/10.1021/jp0557722
Department(s)
Chemistry
International Standard Serial Number (ISSN)
1089-5639
Document Type
Article - Journal
Document Version
Citation
File Type
text
Language(s)
English
Rights
© 2024 American Chemical Society, All rights reserved.
Publication Date
09 Feb 2006
