Electronic Structure and Chemical Bonding of a Highly Stable and Aromatic Auro–Aluminum Oxide Cluster

Abstract

We have produced an auro-aluminum oxide cluster, Au2(AlO)2(-), as a possible model for an Au-alumina interface and investigated its electronic and structural properties using photoelectron spectroscopy and density functional theory. An extremely large energy gap (3.44 eV) is observed between the lowest unoccupied and the highest occupied molecular orbitals of Au2(AlO)2, suggesting its high electronic stability. The global minima of both Au2(AlO)2(-) and Au2(AlO)2 are found to have D2h symmetry with the two Au atoms bonded to the Al atoms of a nearly square-planar (AlO)2 unit. Chemical bonding analyses reveal a strong σ bond between Au and Al, as well as a completely delocalized π bond over the (AlO)2 unit, rendering aromatic character to the Au2(AlO)2 cluster. The high electronic stability and novel chemical bonding uncovered for Au2(AlO)2 suggest that it may be susceptible to chemical syntheses as a stable compound if appropriate ligands can be found.

Theoretical Study on Aluminum Oxide Cluster Anions A12Ox− (x=2−5) with Rhombus Structure

“…As a starting source recommended for achievement of the A1 2 O x − series, [59] the favored A1 2 O 2 − cluster anion usually possesses an open‐shell ground doublet state configuration that can be written as, 1 a g 2 1 b 2 u 2 2 a g 2 1 b 3 u 2 1 b 1 g 2 1 b 1 u 2 2 b 2 u 2 1 b 3 g 2 3 a g 2 2 b 3 u 1 , where the 2 b 3 u orbital is the LUMO of the neutral A1 2 O 2 molecule. In such a way it might be reasonable that the A1 2 O 2 − Al−O bond is elongated by approximately 0.1 Å with respect to the neutral A1 2 O 2 case (1.7 Å), as described in Table 1, in good agreement with the PW91 results [60] …”

“…In such a way it might be reasonable that the A1 2 O 2 À AlÀ O bond is elongated by approximately 0.1 Å with respect to the neutral A1 2 O 2 case (1.7 Å), as described in Table 1, in good agreement with the PW91 results. [60] The totally symmetric vibrational frequencies obtained at our present levels of theory for the anionic cluster are expected to be similar to each other that arise from the structural similarity. Interestingly, upon formation of the 2 A g anion compared to the 1 A g neutral, the intensity of the AlÀ O movements driven by an extra electron were less substantial, based on the available experimental observation (660 � 80 cm À 1 ) and on comparisons with theoretical calculations observed in Table 1.…”

Ultrathin Anion Conductors Based Memristor

“…Therefore, we propose that conductive channels may take main contribution to conduction in MgAl LDH based device, due to aggregation of free ions under bias polarity. [61] Given that the graphene was served as IE in asymmetric electrodes, [62,63] the Schottky barrier played as effective tool for regulating switching and rectifying process were also took into account. [64,65] Low temperature I-V characteristics of LRS were employed (Figure 3f), it was obvious that the conductivity of LDH/graphene contact increased with the rise of temperature, suggesting the enhanced dynamics of mobilities.…”

Gold(III) Mediated Activation and Transformation of Methane on Au1-Doped Vanadium Oxide Cluster Cations AuV2O6+

“…The spin and charge effects on the reactivity of atomic oxygen radical anions (O •– ) on atomic clusters have been revealed. , The extraordinary activity of single noble metal atoms including Au 1 and Pt 1 on metal oxide clusters could also be discovered. , The investigations of the Au 1 -doped metal oxide clusters have demonstrated that the conversions of Au I –O into Au –I –M (M = Ti, Fe, Nb, Ce, and Al) species could drive CO oxidation, dihydrogen activation, and so on . However, possibly because Au III has a high standard reduction potential, the preparation of Au III onto metal oxide clusters was unsuccessful in the previous experiments , and the chemical bonding and reactivity of the important Au III species on metal oxide clusters have been unknown yet.…”