Anion photoelectron spectroscopy of transition metal- and lanthanide metal-silicon clusters: MSin− (n=6–20)

Abstract

The electronic properties of silicon clusters containing a transition or lanthanide metal atom from group 3, 4, or 5, MSi(n), (M=Sc, Ti, V, Y, Zr, Nb, Lu, Tb, Ho, Hf, and Ta) were investigated by anion photoelectron spectroscopy at 213 nm. In the case of the group 3 elements Sc, Y, Lu, Tb, and Ho, the threshold energy of electron detachment exhibits local maxima at n=10 and 16, while in case of the group 4 elements Ti, Zr, and Hf, the threshold energy exhibits a local minimum at n=16, associated with the presence of a small bump in the spectrum. These electronic characteristics of MSi(n) are closely related to a cooperative effect between their geometric and electronic structures, which is discussed, together with the results of experiments that probe their geometric stability via their reactivity to H(2)O adsorption, and with theoretical calculations.

Theoretical study of the structural and electronic properties of aggregates, wires, and bulk phases formed from M@Si16 superatoms (M = Sc−, Ti, V+)

“…We obtained good agreement with the experimental results obtained by Nakajima and coworkers [7][8][9][10][11] for the endohedral character, extra stability, HomoLumo gap, and electron affinity of M@Si 16 clusters. For the ground state geometry of these 68 valence electron clusters, we obtained a distorted FrankKasper T d structure in agreement with previous calculations [12,13].…”

Europium-doped silicon clusters EuSi n (n = 3–11) and their anions: structures, thermochemistry, electron affinities, and magnetic moments

“…There have been some previous studies on silicon clusters. On the experimental aspect, Nakajima et al [25][26][27] investigated first the geometric and the electronic structures of LnSi n − (Ln = Tb, Ho, Lu, 6 ≤ n ≤ 20) by means of photoelectron spectroscopy (PES) and a chemical-probe method. Then, Bowen et al [22,23] studied the structures and properties of LnSi n − (Ln = Pr, Sm, Eu, Gd, Ho, Yb) by using PES.…”

Small copper-doped silicon clusters CuSin (n = 4–10) and their anions: structures, thermochemistry, and electron affinities

“…Silicon-based clusters have been investigated both experimentally and theoretically because they enable not only miniaturization of electronic devices but also exert control over a wide variety of properties by changing size, shape, and composition [1][2][3][4][5][6][7][8][9][10]. In particular, doping a transition metal atom into silicon clusters can alter the structure of the silicon cage, reduce the chemical activity of the surface dangling bonds and enhance stability [11][12][13][14][15][16][17][18][19][20].…”