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Main Title: Structural determination of niobium-doped silicon clusters by far-infrared spectroscopy and theory
Author(s): Li, Xiaojun
Claes, Pieterjan
Härtelt, Marko
Lievens, Peter
Janssens, Ewald
Fielicke, André
Type: Article
Language Code: en
Abstract: In this work, the structures of cationic SinNb+ (n = 4-12) clusters are determined using the combination of infrared multiple photon dissociation (IR-MPD) and density functional theory (DFT) calculations. The experimental IR-MPD spectra of the argon complexes of SinNb+ are assigned by comparison to the calculated IR spectra of low-energy structures of SinNb+ that are identified using the stochastic 'random kick' algorithm in conjunction with the BP86 GGA functional. It is found that the Nb dopant tends to bind in an apex position of the Si-n framework for n = 4-9 and in surface positions with high coordination numbers for n = 10-12. For the larger doped clusters, it is suggested that multiple isomers coexist and contribute to the experimental spectra. The structural evolution of SinNb+ clusters is similar to V-doped silicon clusters (J. Am. Chem. Soc., 2010, 132, 15589-15602), except for the largest size investigated (n = 12), since V takes an endohedral position in Si12V+. The interaction with a Nb atom, with its partially unfilled 4d orbitals leads to a significant stability enhancement of the Si-n framework as reflected, e.g. by high binding energies and large HOMO-LUMO gaps.
Issue Date: 2016
Date Available: 24-Oct-2017
DDC Class: 540 Chemie und zugeordnete Wissenschaften
Sponsor/Funder: EC/FP7/226716/EU/European Light Sources Activities - Synchrotrons and Free Electron Lasers/ELISA
DFG, FOR 1282, Controlling the electronic structure of semiconductor nanoparticles by doping and hybrid formation
Journal Title: Physical chemistry, chemical physics
Publisher: Royal Society of Chemistry
Publisher Place: Cambridge
Volume: 18
Issue: 8
Publisher DOI: 10.1039/c5cp07298k
Page Start: 6291
Page End: 6300
EISSN: 1463-9084
ISSN: 1463-9076
Appears in Collections:FG Lasermolekülspektroskopie und Umweltphysik » Publications

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