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Please use this identifier to cite or link to this item: http://hdl.handle.net/1942/11749

Title: Bonding in negative ions: the role of d orbitals in the heavy analogues of pyridine and furan radical anions
Authors: HAJGATO, Balazs
De Proft, Frank
Szieberth, Denes
Tozer, David J.
DELEUZE, Michael
Geerlingsa, Paul
Nyulaszi, Laszlo
Issue Date: 2011
Citation: PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 13(4). p. 1663-1668
Abstract: We have used a potential wall method to investigate the role of d orbitals in the a(2) singly-occupied molecular orbitals of (2)A(2) negative ion states of two molecular series: pyridine, phosphabenzene, arsabenzene, stibabenzene (C5H5X, X = {N, P, As, Sb}), and furan, thiophene, selenophene, tellurophene (C4H4X, X = {O, S, Se, Te}). Unlike for the lower lying doubly occupied orbitals, heteroatom d-carbon p in-phase (bonding) interactions in these a(2) orbitals are clearly identified and explain the 0.5 eV stabilization of the (2)A(2) radical anion state in those compounds where the heteroatoms have d orbitals in the valence shell, compared to compounds where d orbitals are missing in the valence shell of the heteroatoms. The performance of both the potential wall approach and the approximate expression of Tozer and De Proft for calculating negative electron affinities has been also investigated, through a comparison with results obtained using electron-transmission spectroscopy experiments.
Notes: [Hajgato, Balazs; De Proft, Frank; Geerlingsa, Paul] Vrije Univ Brussel, Eenheid Algemene Chem ALGC, B-1050 Brussels, Belgium. [Hajgato, Balazs; Deleuze, Michael S.] Hasselt Univ, Res Grp Theoret Chem, Dept Chem, B-3590 Diepenbeek, Belgium. [Szieberth, Denes; Nyulaszi, Laszlo] Budapest Univ Technol & Econ, Dept Inorgan & Analyt Chem, H-1521 Budapest, Hungary. [Tozer, David J.] Univ Durham, Dept Chem, Durham DH1 3LE, England. [Nyulaszi, Laszlo] Budapest Univ Technol & Econ, Hungarian Acad Sci, Mat Struct & Modeling Res Grp, H-1111 Budapest, Hungary. hajgato@vub.ac.be
URI: http://hdl.handle.net/1942/11749
DOI: 10.1039/c0cp01151g
ISI #: 000286056400047
ISSN: 1463-9076
Category: A1
Type: Journal Contribution
Validation: ecoom, 2012
Appears in Collections: Research publications

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