Geometric structures and electron affinities of chlorine-doped silicon clusters

Abstract

The electronic and geometrical structures of the ground and possible low-lying isomers of Si n Cl and Si n Cl -(n ¼ 1-6) were investigated at the B3LYP/6-31G(d) and B3LYP/6-311þG(d) levels. The natural populations and natural electron configurations are presented and discussed for the most stable structures. The impact of internal electron transfer between the Si À n (Si n ) subsystem and the Cl atom of Si n Cl À (Si n Cl) clusters is investigated. Furthermore, the three different types of electron affinities for all chlorine-doped silicon clusters are reported, and the dissociation energies are also evaluated for both series using Møller-Plesset and coupled cluster methods.

Neutral 4π-electron tetrasilacyclobutadiene contains unusual features of a Möbius-type aromatic ring

“…Further, the Si1-Cl1 distance with a value of 2.172 Å correlates well with other already reported compounds containing a Si-Cl bond. 31 For 2, we obtained red blockshaped crystals suitable for XRD experiments from a saturated Et 2 O solution. In the asymmetric unit, one molecule is found, featuring the triclinic space group P. The two central silicon atoms together with one phosphorus and two carbon atoms form a ve-membered ring.…”

“…The 1 H and 13 C NMR spectra of 3 are fully consistent with structural composition. 31 P NMR spectrum of compound 3 exhibits a sharp singlet at 4.95 ppm illustrating the presence of a symmetrical pair of -P( i Pr) 2 groups (Figure S13). Its 29 Si NMR spectrum shows a doublet resonance at δ -93.71(J Si-P = 27 Hz) and a triplet at δ 51.31(J Si-P = 17 Hz), which are signi cantly shifted up eld and down eld compared to the reported Si4 ring (D; δ -70.8, 32.2) 43 (Figure S14).…”