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Ab initio Calculations on Bismuth Cluster Polycations
KTH, Superseded Departments, Chemistry.
KTH, Superseded Departments, Chemistry.
KTH, Superseded Departments, Chemistry.ORCID iD: 0000-0001-6737-8233
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2001 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 7, no 13, 2821-2828 p.Article in journal (Refereed) Published
Abstract [en]

Ab initio calculations on bismuth polycationic species of the types Bi-n((n-2)+), Bi-n((n-4)+), and Bi-n((n-6)+) (n = 3 -12) were performed at the Hartree -Fock and density functional theory levels in order to investigate their general properties and the applicability of Wade's rules on bismuth polycations. Some exceptions to Wade's rules were encountered, and, moreover, several predicted and calculated minima shaw only meta-stable behavior. The bonding in bismuth polycations is characterized by a high degree of electron delocalization and "three-dimensional aromaticity".

Place, publisher, year, edition, pages
2001. Vol. 7, no 13, 2821-2828 p.
Keyword [en]
ab initio calculations; bismuth; cluster compounds; ELF (electron localization function)
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-5067DOI: 10.1002/1521-3765(20010702)7:13<2821::AID-CHEM2821>3.0.CO;2-YISI: 000169765800013OAI: oai:DiVA.org:kth-5067DiVA: diva2:7772
Note
QC 20100825Available from: 2005-04-26 Created: 2005-04-26 Last updated: 2017-12-05Bibliographically approved
In thesis
1. On the nature of main-group polycations: an odyssey
Open this publication in new window or tab >>On the nature of main-group polycations: an odyssey
2005 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Compounds containing main-group clusters, with focus on bismuth polycations, have been synthesized and characterized using X-ray diffraction and spectroscopic methods.

Six new compounds have been isolated from synthesis in GaX3-arene media; Bi8[GaCl4]2, Bi8 [GaBr4]2, Sb8[GaCl4]2, Sb8[GaBr4]2, Te4[Ga2Cl7]2 and Te4[Ga2Br7]2. Sb2+ 8 is the first homopolyatomic antimony cation to be isolated. The cation forms a square antiprism, in correlation with Wade’s rules, and displays a significant difference in length between the inter-square and intra-square Sb–Sb distances. The geometries of the Sb2+ 8 cations in Sb8[GaCl4]2 and Sb8[GaBr4]2 are in excellent agreement; the average intra-square and intersquare Sb–Sb distances are 2.87 Å and 2.97 Å, respectively.

A very strong Raman band attributed to Sb2+8 is found at 180 cm-1. The Bi2+8 (square antiprismatic) and Te2+4 (squareplanar) polycations are known from earlier compounds. The Bi–Bi distances in Bi8[GaCl4]2 (3.07–3.12 Å) are in general agreement with previous structures, while the Bi–Bi distances of Bi8[GaBr4]2 (2.92–3.18 Å) display a wider distrubution than previously observed. The Te–Te distances of the cations of Te4[Ga2Cl7]2 and Te4[Ga2Br7]2 are 2.66 and 2.67 Å, respectively.

Quantum chemical calculations on bismuth polycations show that all species predicted byWade’s rules are local minima on a potential energy surface. The cation–anion interactions have been considered for salts containing bismuth polycations and it has been confirmed that such interactions have a major influence on the polycation stability.

The new compound Bi16I4 has been isolated from molten Bil3. The structure consists of polymerized Bi16I4 molecules forming infinite ribbons and is very similar to the structure of the known metal-rich bismuth iodides, Bi14I4 and Bi18I4.

DFT calculations predict all three compounds to be metallic conductors, while Bi4I4 is a semiconductor.

Place, publisher, year, edition, pages
Stockholm: KTH, 2005. x, 104 p.
Series
Trita-OOK, ISSN 0348-825X ; 1077
Keyword
Chemistry, Inorganic chemistry, Kemi
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-178 (URN)91-7178-000-9 (ISBN)
Public defence
2005-04-29, sal D3, Lindstedtsvägen 5, Stockholm, 13:00 (English)
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Note
QC 20101021Available from: 2005-04-26 Created: 2005-04-26 Last updated: 2010-10-21Bibliographically approved

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