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Issue 19, 2000
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Ab initio G2 and DFT calculations on electron affinity of cyclopentadiene, silole, germole and their 2,3,4,5-tetraphenyl substituted analogs: structure, stability and EPR parameters of the radical anions

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Abstract

Energies, geometries and electronic structures of cyclopentadiene (1), silole (2), germole (3) and their radical anions (RAs) 1a3a have been studied by quantum-chemical methods at the G2(MP2, SVP) and DFT B3LYP/6-31G(d,p) levels. According to G2(MP2, SVP) calculations 13 have negative electron affinities (EAs) equal to −1.09, −0.06 and −0.15 eV, respectively, and hence their RAs are unstable in the gas phase. 1,2,3,4-Tetraphenylcyclopenta-1,3-diene (4) and 2,3,4,5-tetraphenylsubstituted-2 (5) and 3 (6) and their radical anions (4a6a) were studied at the B3LYP/6-31G(d)//AM1 level. Substitution of cyclodienes results in significant stabilization of RAs 46 because of the effective delocalization of an extra electron within phenyl groups, especially those in positions 2 and 5, so 46 all have a positive EA. Our best estimates give for 4, 5 and 6 EA values 0.98, 1.30 and 1.13 eV respectively. The calculated hyperfine coupling (hfc) constants a(H) for radical anions 4a6a are in a good agreement with experimental values. Variation of group 14 element (C, Si, Ge) in the series 13 and 46 do not produce a monotonous change of EA and hfc values.

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Publication details

The article was received on 30 Jun 2000, accepted on 26 Jul 2000 and first published on 08 Sep 2000


Article type: Paper
DOI: 10.1039/B005247G
Citation: Phys. Chem. Chem. Phys., 2000,2, 4293-4297
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    Ab initio G2 and DFT calculations on electron affinity of cyclopentadiene, silole, germole and their 2,3,4,5-tetraphenyl substituted analogs: structure, stability and EPR parameters of the radical anions

    V. I. Faustov, M. P. Egorov, O. M. Nefedov and Y. N. Molin, Phys. Chem. Chem. Phys., 2000, 2, 4293
    DOI: 10.1039/B005247G

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