Electronic Structure and Stability of [BX] (X = F-At): A Combined Photoelectron Spectroscopic and Theoretical Study.
The stability and electron loss process of numerous multiply charged anions (MCAs) have been traditionally explained in terms of the classical Coulomb interaction between spatially separated charged groups. An understanding of these processes in MCAs with not wellseparated excess charges is still la...
| Publicado en: | Journal of the American Chemical Society Vol. 139; no. 41; pp. 14749 - 14757 |
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| Autores principales: | , , , , , , , , |
| Formato: | Artículo |
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American Chemical Society
10/18/2017
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=125891806&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 125891806 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 10/18/2017 vid: 139 iid: 41 pid: 997 pub: American Chemical Society artinfo: ui: 125891806 10.1021/jacs.7b08598 ppf: 14749 ppct: 8 formats: tig: atl: Electronic Structure and Stability of [BX] (X = F-At): A Combined Photoelectron Spectroscopic and Theoretical Study. aug: au: Warneke, Jonas Gao-Lei Hou Aprà, Edoardo Jenne, Carsten Zheng Yang Zhengbo Qin Kowalski, Karol Xue-Bin Wang Xantheas, Sotiris S. affil: Physical Sciences Division, Pacific Northwest National Laboratory, 902 Battelle Boulevard, P.O. Box 999, MS K8-88, Richland, Washington 99352, United States Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352 United States Anorganische Chemie, Fakultät für Mathematik und Naturwissenschaften, Bergische Universität Wuppertal, Gaußstraße 20, 42119 Wuppertal, Germany Advanced Computing, Mathematics and Data Division, Pacific Northwest National Laboratory, 902 Battelle Boulevard, P.O. Box 999, MS K1-83, Richland, Washington 99352, United States Department of Chemistry, University of Washington, Seattle, Washington 98195, United States su: Electronic structure Photoelectron spectrometers Anions spectra Density functional theory Crystal structure sug: subj: Electronic structure Photoelectron spectrometers Anions spectra Density functional theory Crystal structure ab: The stability and electron loss process of numerous multiply charged anions (MCAs) have been traditionally explained in terms of the classical Coulomb interaction between spatially separated charged groups. An understanding of these processes in MCAs with not wellseparated excess charges is still lacking. We report the surprising properties and physical behavior of [BX], X = F, Cl, Br, I, At, which are MCAs with not well-separated excess charges and cannot be described by the prevailing classical picture. In this series of MCAs, comprising a "boron core" surrounded by a "halogen shell", the sign of the total charge in these two regions changes along the halogen series from X = F-At. With the aid of experimental photoelectron spectroscopy and highly correlated ab initio electronic structure calculations, we demonstrate that the trend in the electronic stability of these MCAs is determined by the interplay between the Coulomb (de)stabilization originating from the "boron core" and "halogen shell" and the extension of the overlap between the orbitals from both regions. The second excess electron is always taken from the most positively charged region, viz., the "boron core" for X = F, Cl, and the surrounding "halogen shell" for X = I, At. This change in the physical behavior is attributed to the position of the highest occupied molecular orbital, which dwells in a region that is spatially separated from the one containing the excess negative charge. The unusual intrinsic electronic structure of the [BX] MCAs provides the basis for a molecular level understanding of their observed unique physical and chemical properties and a new paradigm for understanding the properties of these MCAs with not well-separated charges that departs from the prevailing model used for spatially separated charges that is based on their classical Coulomb interaction. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2017 holdings: @attributes: islocal: N |
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