Theoretical study of Al(n) and Al(n)O (n = 2-10) clusters.
The stable structures, energies, and electronic properties of neutral, cationic, and anionic clusters of Al(n) (n = 2-10) are studied systematically at the B3LYP/6-311G(2d) level. We find that our optimized structures of Al5(+), Al9(+), Al9(-), Al10, Al10(+), and Al10(-) clusters are more stable than the corresponding ones proposed in previous literature reports. For the studied neutral aluminum clusters, our results show that the stability has an odd/even alternation phenomenon. We also find that the Al3, Al7, Al7(+), and Al7(-) structures are more stable than their neighbors according to their binding energies. For Al7(+) with a special stability, the nucleus-independent chemical shifts and resonance energies are calculated to evaluate its aromaticity. In addition, we present results on hardness, ionization potential, and electron detachment energy. On the basis of the stable structures of the neutral Al(n) (n = 2-10) clusters, the Al(n)O (n = 2-10) clusters are further investigated at the B3LYP/6-311G(2d), and the lowest-energy structures are searched. The structures show that oxygen tends to either be absorbed at the surface of the aluminum clusters or be inserted between Al atoms to form an Al(n-1)OAl motif, of which the Al(n-1) part retains the stable structure of pure aluminum clusters.
Probing the structural and electronic properties of small aluminum dideuteride clusters.
Adsorption of deuterium on the neutral and anionic Aln(λ) (n=1-9, 13; λ=0, -1) clusters has been investigated systematically using density functional theory. The comparisons between the Franck-Condon factor simulated spectra and the measured photoelectron spectroscopy (PES) of Cui and co-workers help to search for the ground-state structures. The results showed that D2 molecule tends to be dissociated on aluminum clusters and forms the radial AlD bond with one aluminum atom. By studying the evolution of the binding energies, second difference energies and HOMO-LUMO gaps as a function of cluster size, we found Al2D2, Al6D2 and Al7D2(̄) clusters have the stronger relative stability and enhanced chemical stability. Also, considering the larger adsorption energies of these three clusters, we surmised that Al2, Al6 and Al7(̄) may be the better candidates for dissociative adsorption of D2 molecule among the clusters we studied. Furthermore, the natural population analysis (NPA) and difference electron density were performed and discussed to probe into the localization of the charges and reliable charge-transfer information in AlnD2 and AlnD2(̄) clusters.
Vertebral Fusion in Two Early Jurassic Sauropodomorph Dinosaurs from the Lufeng Formation of Yunnan, China
Here we describe two instances of pathological vertebral fusion in two genera of sauropodomorph dinosaurs from the Early Jurassic Lufeng Formation in Yunnan, China. The first is a specimen, of Lufengosaurus huenei with two fused cervical vertebrae, and the other is a specimen of the Lufeng basal sauropod, with two fused caudal vertebrae. Both pathologies are consistent with spondyloarthropathy and represent the earliest known occurrence of that disease in dinosaurs. The two specimens affirm that early dinosaurs suffered from the same bone diseases as living vertebrates. Spondyloarthropathy in these dinosaurs may have been induced by long-term mechanical stress, such as weight bearing, and/or limited motion at the joint that would otherwise have inhibited such remodeling. In both cases, surface remodeling suggests that the animals survived well beyond the initiation of spondyloarthropathy.