Photoelectron spectroscopy and density functional calculations of CuSin− (n = 4–18) clusters

Abstract

We conducted a combined anion photoelectron spectroscopy and density functional theory study on the structural evolution of copper-doped silicon clusters, CuSi(n)(-) (n = 4-18). Based on the comparison between the experiments and theoretical calculations, CuSi(12)(-) is suggested to be the smallest fully endohedral cluster. The low-lying isomers of CuSi(n)(-) with n ≥ 12 are dominated by endohedral structures, those of CuSi(n)(-) with n < 12 are dominated by exohedral structures. The most stable structure of CuSi(12)(-) is a double-chair endohedral structure with the copper atom sandwiched between two chair-style Si(6) rings or, in another word, encapsulated in a distorted Si(12) hexagonal prism cage. CuSi(14)(-) has an interesting C(3h) symmetry structure, in which the Si(14) cage is composed by three four-membered rings and six five-membered rings.

Photoelectron velocity-map imaging signature of structural evolution of silver-doped lead Zintl anions

“…2), which is similar to the favorable structures of Na@Sn 5 0/− , 24 Cu@Si 5 − , 47 and Ag@Si 5 . 51 The VDE of 5A is calculated to be 2.45 eV, which is in accord with the experimental value of 2.49 eV (Table I).…”

“…Interestingly, silver-doped lead Zintl anions have been found to undergo a transition between square pyramid and pentagonal pyramid molecular structures at n = 11. In contrast, the endohedral structure for Cu@Si n − is formed at n = 12, 47 in which the copper atom is encapsulated in a distorted hexagonal prism cage. The difference in the diameter of the cage may be responsible for such different structural pattern, and the related systematical exploration would benefit the rational design cluster-assembled materials with continuously tunable physical and/or chemical properties.…”

“…Recent study on the Cu@Si n − (n = 4-18) clusters 47 indicates that Cu@Si 12 − is the smallest fully endohedral cluster, in which the copper atom is encapsulated in a distorted hexagonal prism cage, different from the M@Sn 12 − cluster anions. 35 Here, we report a study on the structural evolution of the Ag@Pb n − (n = 5-12) Zintl anions using photoelectron velocity-map imaging spectroscopy and quantum chemical calculation.…”

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

“…Like carbon atoms, they can appear with sp, sp 2 , or sp 3 hybridization in compounds [11,12]. However, a wide variety of experimental [13][14][15] and theoretical [16][17][18] research works elucidated that doping a suitable foreign atom inside silicon clusters can not only enhance the stability, but also influence profoundly the electron properties of these complexes. In particular, the examples of encapsulating a transition metal (TM) atom insider silicon clusters as building blocks of cluster-assembled materials with novel magnetic, electronic, and possibly optical properties are numerous.…”

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

“…Fielicke and coworkers [25,26] tested the far-infrared vibrational spectra of CuSi n + (n = 6-11) employing an argon-tagging infrared multiple photon dissociation technique. Recently, Xu et al [27] measured the EAs of CuSi n (n = 4-18) using photoelectron spectroscopy.…”