Photoelectron spectroscopy and density functional calculations of AgSin− (n = 3–12) clusters

Abstract

We investigated the structural evolution and electronic properties of AgSi(n)(-) (n = 3-12) clusters using anion photoelectron spectroscopy and density functional theory calculations. The vertical detachment energies and adiabatic detachment energies of AgSi(n)(-) (n = 3-12) clusters were estimated from their photoelectron spectra. The structures of the AgSi(n)(-) (n = 3-12) clusters were tentatively assigned based on the comparison of theoretical calculations and experimental measurements. The studies show that the structures of AgSi(n)(-) (n = 3-12) clusters are dominated by exohedral structures with the Ag atom occupying the low coordinated sites. No endohedral structure has been found for AgSi(n)(-) clusters with n ≤ 12.

The Geometric Structure of Silver‐Doped Silicon Clusters

“…The Si framework of Si14Ag + differs from that of Si14 + , [27] but still the Ag atom prefers to cap an edge. Most of the assigned structures of cationic SinAg + (n = 6-12) in the present work are not identical to those assigned for anionic SinAg − (n = 6-12) by Kong et al, [33] but there is a general agreement in that the Ag atom prefers to be exohedral with a low coordinated position. The different charge states may explain the structural differences.…”

“…Recently, Kong et al investigated the structural evolution and electronic properties of SinAg − (n = 3−12) using anion photoelectron spectroscopy in combination with DFT calculations and found that those clusters have exohedral structures with the Ag atom occupying a low coordinated site. [33] These contradicting findings demonstrate that, as yet, there is no conclusive understanding of the geometric structure of small Ag doped Sin clusters and the effect of Ag binding to Sin +/0/− needs to be clarified. In the present work, the geometric structures of SinAg + (n = 6−15) clusters are assigned by a combination of the experimental and theoretical investigations.…”

“…[11] Compared with the bonding between Cu and Si atoms, the weaker Ag-Si bonds may account for the different growth patterns for larger sized SinAg + and SinCu + (n = 12-15) with the Si atoms preferring to form bonds with each other instead of the Ag atom. [33] …”

Structures, Stabilities, and Electronic Properties of Small-Sized Zr2Si n (n=1–11) Clusters: A Density Functional Study

“…Oharaa et al [16] reported experimental evidence for the geometric and electronic structures of metal-encapsulating Si cage cluster ions TMSi n -(TM = Ti, Hf, Mo, and W; n = [8][9][10][11][12][13][14][15][16][17][18] and found that the electron affinity of TMSi n shows local minima around n = 15-16. Koyasu et al [17] investigated the electronic properties of MSi n (M = Sc, Ti, V, Y, Zr, Nb, Lu, Tb, Ho, Hf, and Ta; n = [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] clusters using the anion photoelectron spectroscopy at 213 nm. The results indicated that ScSi 16 -, TiSi 16 , VSi 16 + , NbSi 16 + , and TaSi 16 + are generated in large quantities due to both electronic and geometric closings.…”

“…The results indicated that ScSi 16 -, TiSi 16 , VSi 16 + , NbSi 16 + , and TaSi 16 + are generated in large quantities due to both electronic and geometric closings. Kong et al [18] explored the structural evolution and electronic properties of anionic silver-doped silicon clusters, AgSi n -(n = 3-12), using anion photoelectron spectroscopy and found that the structures of AgSi n -clusters are dominated by exohedral structures with the Ag atom occupying the low coordinated sites.…”