Electronic Structure of Al₃O_n and Al₃O_n^- (n = 1−3) Clusters

Abstract

Density functional, quadratic configuration interaction and electron propagator calculations have yielded structures, isomerization energies, and anion vertical electron detachment energies pertaining to Al 3 O nand Al 3 O n , where n ) 1, 2, or 3. These data suffice for an accurate assignment of recent anion photoelectron spectra. Peaks whose relative intensities vary with experimental conditions of ion preparation and transport are associated with isomers whose energies are close to those of the lowest singlet structures. Dyson orbitals associated with the lowest electron detachment energies are dominated by Al-centered functions with antibonding relationships to nearby O centers.

An efficient, renormalized self‐energy for calculating the electron binding energies of closed‐shell molecules and anions

“…In addition, more intense peaks have been reported in several papers and the unusual phenomenon of anion photoisomerization has been confirmed [12][13][14]. Optimizations of a large number of ground-state structures yielded two isomers with nearly identical total energies [15]. These minima, designated the book and kite, may be expected to have vertical electron detachment energies that correspond to the peaks of the experimental spectrum.…”

“…To obtain a consistent interpretation of the experiments, it was necessary in previous studies [15] to employ an advanced electron propagator technique (BD-T1 [1]) based on a Brueckner doubles, coupled-cluster reference state and a full, renormalized treatment of the 2ph plus 2hp operator manifold. The BD-T1 results of Table II were obtained with the 6-311ϩG(2df ) basis set.…”

Photoelectron spectroscopy and density functional theory study of TiAlOy− (y=1–3) and TiAl2Oy− (y=2–3) clusters

“…That is slightly different from the case of Al 3 O 3 and Al 3 O 3 − , whereas the most stable structures for the anion and neutral are different, the kite structure is more stable for Al 3 O 3 while the book structure is more stable for Al 3 O 3 − . 42,45,47 In addition to the kite and book structures, we also found anchor structures for TiAl 2 O 3 neutral ͑Fig. 4, 5BЈ͒ and anion ͑Fig.…”

“…Theoretically, a number of methods were employed to explore the structures and bonding of the clusters of titanium [22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37] and aluminum oxides. [38][39][40][41][42][43][44][45][46][47][48][49][50][51][52][53] Although the clusters of titanium oxide and aluminum oxide were intensively investigated, the study of hybrid titanium-aluminum oxides is quite rare. In the past few years, it has been proposed that hybrid titanium-aluminum oxides might have potential applications as a high-dielectric ͑high-K͒ material for the next generation of complementary metal-oxide-semiconductor ͑CMOS͒ gates.…”

Structural and Electronic Properties of Neutral and Ionic GanOn Clusters with n = 4—7

“…Several initial planar and nonplanar diverse configurations of neutral, anionic, and cationic clusters were considered for these calculations. The choice of some of the initial geometries was partially dependent upon the previous studies of small clusters of aluminum oxide [22][23][24][25][26][27][28] and gallium nitride. 29 It is to be noted here that the linear configurations were not considered here, since our earlier studies find the low-lying isomers of Ga 3 O 3 to be planar configurations.…”