Laser-Evaporated Aluminum Atom Reactions with Halogen Molecules. Infrared Spectra of AlX_n (X = F, Cl, Br, I; n = 1−3) in Solid Argon

Abstract

Reactions of laser-evaporated aluminum atoms with molecular fluorine, chlorine, bromine, and iodine in excess argon during condensation onto a CsI window at 11 ( 1 K produced the AlX n (X ) F, Cl, Br, I and n ) 1-3) and Al 2 X 6 molecules, which were characterized by infrared absorption spectroscopy. Low laser power favored the primary reaction product AlX and AlX 2 transient species over the more stable secondary reaction product AlX 3 molecules. Chlorine and bromine isotopic structures substantiated the molecular identifications and vibrational assignments. DFT calculations were done for the AlCl n and AlBr n series to support the vibrational assignments. Possible Al 2 Cl 4 structures were also explored by DFT calculations, and evidence is presented for a distorted Cl 2 AlCl 2 Al structure. The present study provides further evidence for transient aluminum dihalide radicals for the four halogens.

The Chemical Vapor Deposition of Aluminum Nitride: Unusual Cluster Formation in the Gas Phase

“…In a recent study, Hassanzadeh et al using DFT mentioned that the Al-Cl bond lengths for AlCl 3 are slightly inequivalent. 47 In contrast, we obtain a trigonal planar AlCl 3 molecule (D 3h symmetry) at all levels of theory. The theoretical Al-Cl distance is 0.02-0.03 Å longer than reported experimentally.…”

“…The theoretical vibrational frequencies are in good agreement with experimental results obtained in solid argon matrices. 47,50 AlCl has a 1 Σ + electronic ground state. The Al-Cl distance is further increased compared to AlCl 2 .…”

G2(MP2) Molecular Orbital Study of [H3AlXH3]- (X = C, Si, and Ge) and H3AlYH3 (Y = N, P, and As) Complexes

“…The Friedel−Crafts alkylation and acylation of aromatic rings, removal of tert -butyl groups from phenols, and the well-known Ziegler−Natta polymerization reactions are some examples in which the aluminum trichloride acts as catalyst. Many of these important compounds have been experimentally and theoretically studied extensively. − Recently, Andrews et al have published an interesting work concerning the reaction of laser-evaporated aluminum atom with molecular fluorine, chlorine, bromine, and iodine leading to mono-, di-, and trihalide aluminum. Vibrational spectroscopy and computational geometries of these aluminum halides are well-known.…”

High‐Energy SWCNT Cathode for Aqueous Al‐Ion Battery Boosted by Multi‐Ion Intercalation Chemistry

“…The intercalated ions at −0.05 and 0.2 V versus Ag/AgCl were still confirmed to be the mixture of Al 3+ and H + rather than Cl – by EQCM (Figure 6c), indicating the assisted function of Cl – . To further reveal the Cl‐assisted intercalation behavior, the SWCNT cathode at charged and discharged stages in WIS‐AlCl 3 was examined by FTIR test (Figure 4e), where ClAl bond signal occurred at 461, 755, and 957 [ 25 ] cm –1 . The peaks show clear peaks at both charged and discharged states in the WIS‐AlCl 3 electrolyte, while they are not shown in other electrolytes, suggesting the effect of Cl.…”