Vibrational spectroscopy of neutral silicon clusters via far-IR-VUV two color ionization

Fielicke, André; Lyon, Jonathan T.; Haertelt, Marko; Meijer, Gerard; Claes, Pieterjan; Haeck, Jorg De; Lievens, Peter

doi:10.1063/1.3262803

Cited by 72 publications

(100 citation statements)

References 39 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…It is instructive to compare the properties of Si6B with those of Si7 [25,27] to evaluate the effects of SiB substitution on the geometric, vibrational, and electronic properties. To this end, Figure 5 shows the vibrational spectra and geometric structures of Si7 and its B-doped counterpart Si6B.…”

Section: Resultsmentioning

confidence: 99%

“…Surprisingly, no spectroscopic data are available for B-doped silicon clusters in any charge state. Here, we combine infraredultraviolet two-color ionization (IR-UV2CI) spectroscopy [27] with quantum chemical simulations to determine the structure of Si6B, a strategy recently applied to a variety of (doped) silicon clusters [25,[27][28][29][30].…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Characterization of neutral boron-silicon clusters using infrared spectroscopy: The case of Si6B

Trường

Haertelt

Jaeger

et al. 2016

International Journal of Mass Spectrometry

Self Cite

View full text Add to dashboard Cite

Nano-size clusters are of great interest for understanding of fundamental properties and processes relevant for applied materials science such as heterogeneous catalysis. In this study, we present a newly developed dualtarget dual-laser ablation source, suitable for the production of binary clusters and their spectroscopic characterization. With the current design, an almost arbitrary mixing ratio can be achieved by altering different parameters such as the laser fluences. Boron and silicon targets are chosen for cluster production, illustrating the possibility to control the outcome ranging from pure boron over mixed SinBm to pure silicon clusters. As a test system, Si6B clusters are characterized by means of infrared-ultraviolet two-color ionization (IR-UV2CI) spectroscopy, combined with quantum chemical simulations. The most stable structure of Si6B (Cs, 2 A') predicted in our previous work is confirmed by the present experiment. Doping of Si7 with a single B atom has a drastic impact on the geometric, vibrational, and electronic properties.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Characterization of neutral boron-silicon clusters using infrared spectroscopy: The case of Si6B

Trường

Haertelt

Jaeger

et al. 2016

International Journal of Mass Spectrometry

Self Cite

View full text Add to dashboard Cite

show abstract

“…In cases where several isomers may contribute, only the calculated lowestenergy structure is taken for evaluating the relative stability. The structures of the bare Si n + and Si n (n = 4-12) clusters are taken from previous experimental and theoretical studies, 9,12,[67][68][69][70] and then are reoptimized at the BP86/def-SVP level of theory. Fig.…”

Section: Relative Stability Of the Doped Clustersmentioning

confidence: 99%

Structural determination of niobium-doped silicon clusters by far-infrared spectroscopy and theory

Claes

Haertelt

et al. 2016

Phys. Chem. Chem. Phys.

Self Cite

View full text Add to dashboard Cite

In this work, the structures of cationic Si n Nb + (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 Si n Nb + are assigned by comparison to the calculated IR spectra of low-energy structures of Si n Nb + 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 Si n Nb + 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 Si 12 V + . 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.

show abstract

“…week ending 21 OCTOBER 2011 spectra are based on calculated harmonic vibrational frequencies using Gaussian line width broadening (5 cm À1 FWHM) and by scaling the frequencies with a constant multiplication factor of 1.03, consistent with our earlier work [30][31][32][33]. Structural assignment is done by comparing the IR-MPD spectra with calculated vibrational spectra of the lowest lying isomers.…”

mentioning

confidence: 99%

“…Geometry optimizations are performed by using the pure BP86 functional [28,29], in conjunction with the 6-311þGðdÞ basis set. This methodology was successful in evaluating IR spectra of bare Si þ n (n ¼ 6-21) [30], Si 0 n (n ¼ 6; 7; 10) [31], and exohedrally doped Si n X þ (X ¼ V; Cu; n ¼ 4-11) clusters [32,33]. Initial atomic configurations are selected on the basis of structures reported in literature and by substitution or addition of a V atom to bare silicon clusters [30].…”

mentioning

confidence: 99%

Structural Identification of Caged Vanadium Doped Silicon Clusters

et al. 2011

View full text Add to dashboard Cite

The geometry of cationic silicon clusters doped with vanadium, Si n V þ (n ¼ 12-16), is investigated by using infrared multiple photon dissociation of the corresponding rare gas complexes in combination with ab initio calculations. It is shown that the clusters are endohedral cages, and evidence is provided that Si 16 V þ is a fluxional system with a symmetric Frank-Kasper geometry. DOI: 10.1103/PhysRevLett.107.173401 PACS numbers: 36.40.Mr, 33.20.Ea, 61.46.Bc The ongoing trend towards further miniaturization in microelectronics triggers a quest for nanostructured building blocks. Given the importance of silicon in the semiconductor industry, it is straightforward to consider small silicon particles for nanostructuring. The search for silicon building blocks was initiated in the 1990s and revealed strong size dependencies and cluster geometries that do not correspond to bulk fragments [1]. Unfortunately, elemental silicon clusters have dangling bonds, which renders them chemically reactive and therefore not suitable as nanoscale building blocks [2]. In contrast to carbon, silicon prefers the formation of bonds through sp 3 hybridization, resulting in three-dimensional structures [3]. Ion mobility studies demonstrated that silicon structures follow a prolate growth sequence and no fullerenelike caged particles are formed [4,5]. However, incorporating a metal atom or hydrogenation can saturate the dangling bonds and induce the formation of caged silicon clusters [3,6,7].Theoretical investigations of doped silicon clusters have considered dopants from almost every group of the periodic table [6]. Most interestingly, it is predicted that transition-metal atoms possibly stabilize the clusters and induce the formation of symmetric endohedral cages with the dopant atom at the center of the cage, which is of relevance for novel silicon based nanostructured devices [8][9][10][11][12]. For example, fullerenelike cages and Frank-Kasper (FK) polyhedrons, which are tetrahedrally close-packed structures containing interpenetrating polyhedra with coordination numbers 12, 14, 15, or 16 [13], are predicted for Ti and V doped silicon clusters with at least 12 Si atoms [10,14,15]. However, if there are insufficient Si atoms to fully enclose the dopant atom, basketlike structures are formed [11]. Although mass spectrometry and photodissociation experiments [8,[16][17][18][19] show an enhanced stability of specific transition-metal doped silicon clusters, no single experiment has yet provided detailed information on their structure. Up to now, mainly indirect evidence is found for the formation of symmetric species by photoelectron and x-ray spectroscopy studies [20][21][22] and chemical probe methods [20,23].In this Letter, the structure of size selected endohedrally doped silicon clusters is obtained by combining experimental infrared multiple photon dissociation (IR-MPD) spectroscopy with quantum chemical calculations. It will be shown that the V dopant atom in the cationic Si n V þ (n ¼ 12-16) clusters locates at the center ...

show abstract

Vibrational spectroscopy of neutral silicon clusters via far-IR-VUV two color ionization

Cited by 72 publications

References 39 publications

Characterization of neutral boron-silicon clusters using infrared spectroscopy: The case of Si6B

Characterization of neutral boron-silicon clusters using infrared spectroscopy: The case of Si6B

Structural determination of niobium-doped silicon clusters by far-infrared spectroscopy and theory

Structural Identification of Caged Vanadium Doped Silicon Clusters

Contact Info

Product

Resources

About