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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 | Publisher: | ROYAL SOC CHEMISTRY | Source: | 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 | Document URI: | http://hdl.handle.net/1942/11749 | ISSN: | 1463-9076 | e-ISSN: | 1463-9084 | DOI: | 10.1039/c0cp01151g | ISI #: | 000286056400047 | Category: | A1 | Type: | Journal Contribution | Validations: | ecoom 2012 |
Appears in Collections: | Research publications |
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