The DFT Quantum Chemistry Study of Hexafluorobenzene

Abstract:

The molecular structures, electron affinities, and dissociation energies of the C₆F₆ molecule have been determined using seven hybrid and pure density functional theory (DFT) methods and the DZP++ basis set. Three different types of the neutral-anion energy separations reported in this work are the adiabatic electron affinity (EA_ad), the vertical electron affinity (EA_vert), and the vertical detachment energy (VDE). The most reliable adiabatic electron affinities, obtained at the B3PW91 and B3LYP levels, are 0.59 and 0.69 eV, respectively. The first dissociation energies D_e (C₆F5-F) for the neutral C₆F₆ predicted by the DFT metho_{Subscript text}ds except BHLYP are 5.195.44 eV. Compared with the limited experimental dissociation energies, our theoretical predictions of the B3LYP and B3PW91 methods are fairly reasonable.

• Periodical: Advanced Materials Research (Volumes 610-613)
• Pages: 106-110
• DOI: https://doi.org/10.4028/www.scientific.net/AMR.610-613.106
• Online since: December 2012
• Authors: Hui Yi Pei, Ai Fang Gao, Zhen Ya Zhu
• Keywords: DFT, Dissociation Energies, Electron Affinities, Geometries, Hexafluorobenzene

References

[1] Xie Y.M, Schaefer H. F, Cotton F.A, Chem. Commun. 1(2003) 102.

[2] Christophorou L.G, Datskos P.G, Int. J. Mass Spectrom. Ion Processes 149/150 (1995) 59.

[3] Dillow G.W, Kebarle P, Substituent effects on the electron affinities of perfluorobenzenes C6F5X [J]. J. Am. Chem. Soc, 1989, 111(15): 5592-5596.

DOI: 10.1021/ja00197a014

[4] Ervin K.M, Anusiewicz I, Skurski P, Simons J, Lineberger W.C, The Only Stable State of O2- Is the X2Pg Ground State and It (Still!) Has an Adiabatic Electron Detachment Energy of 0.45 eV [J]. J. Phys. Chem. A. 2003,107(41): 8521-8529.

DOI: 10.1021/jp0357323

[5] Miller T.M, Doren J. M. V., Viggiano A.A, Int. J. Mass Spectrom. 233 (2004) 67–73.

[6] Kohn W, Becke A. D, Parr R. G, Density Functional Theory of Electronic Structure [J]. J. Phys.Chem, 1996, 100(31): 12974-12980.

DOI: 10.1021/jp960669l

[7] Frisch M J, Trucks G W, Schlegel H B, et al. Gaussian03 quantum chemistry package [M]. Pittsburgh, PA: Gaussian Inc., 2003.

[8] Almenningen A, Bastiansen O, Seip R. and Seip H. M, Acta. Chem. Scand. 18(1964) 2115.

DOI: 10.3891/acta.chem.scand.18-2115

[9] Danten Y, Cabaco M. L, Tassaing T and Besnard M, A structural study of the hexafluorobenzene from liquid to supercritical conditions using neutron diffraction and molecular dynamics [J]. J. Chem. Phys. 2001, 115(9): 4239-4248.

DOI: 10.1063/1.1389292

[10] Cox J. D, Gundry H. A, Harrop D, and Head A. J, J. Chem. Thermodynamics. 1(1969) 77.

[11] Steele D and Wheatley W, J. Mol. Spectry. 32 (1969) 265.

[12] Steele D and Whiffen D. H, Trans. Faraday. Soc. 55(1959) 369.

[13] J. H. S. Green and D. J. Harrison, J. Chem. Thermodynamics. 8(1976) 529.

[14] J. Almlof and Jr. K. Faegri, J. Chem. Phys. 79(1983) 2291.