Density Functional Theory Calculations for the Structural, Electronic, and Magnetic Properties of (Gd₂O₃)_n^0,±1 Clusters with n = 1–10

Abstract

The structural stability and electronic and magnetic properties of stoichiometric (Gd 2 O 3 ) n clusters with n = 1−10 were investigated using spin-polarized density functional theory through the broken-symmetry approach. Size-induced changes in the point symmetry of these clusters were observed. A large coordination number led to elongation of Gd−O bonding. Either adding an electron to or removing an electron from the ground state of a neutral cluster brought significant changes in the van der Waals volume for clusters n = 1−3. Binding energy increased with cluster size. However, the highest occupied molecular orbital−lowest unoccupied molecular orbital gap, ionization, and electron affinity fluctuated when n increased from 1 to 10. Natural population analysis and partial density of states revealed that the Gd-4f orbital hardly participated in bonding and that the Gd-5d/6s/6p orbitals were hybrid with the O-2p orbitals. The competition between Ruderman−Kittel−Kasuya−Yosida-type and superexchange-type interactions resulted in the magnetic oscillation of clusters between antiferromagnetic and ferromagnetic states. We also found similar behavior in the various structures of Gd 12 O 18 . The ground state was easily activated to the excited state because the antiferromagnetic and ferromagnetic coupling states were nearly identical in energy.

Quantum mechanical studies of full‐shell noble metal nanoclusters in water

“…To quantitatively describe the structure properties of NMNCs, their average coordination number (ACN), the average bond length (ABL), and the binding energy (BE) per atom are plotted as the function of metallic nanocluster size in Figure . The ACN is widely used to describe the structure properties of a NC, which is closely associated with the formation of a NC . Note that the NMNCs with the same shells have the same values of ACN.…”

“…From one‐shell M 13 to three‐shell M 147 , there is a gradually raising ACN of 6.461 → 8.509 → 9.468. Generally speaking, a nanostructure with a low ACN has a shorter ABL due to low coulomb repulsion . The rule is also valid for Pd and Pt NCs, as the ABL of these NMNCs slightly grows with increasing ACN.…”

A joint experimental and theoretical Raman study on the interactions of pyridine adsorbed on chemically pure Ag18 clusters

“…This can be evidenced by the weak OPDOS value. In LUMO level, the OPDOS values are negative, indicating that in this region Ag 18 and pyridine have anti‐bonding characters …”

Electronic Structure and Optical Absorption in Gd‐Implanted Silica Glasses

“…Our previous works in the area of oxides doped by transitional metals and gadolinium oxide demonstrate that using of DFT + U methods is not required for these systems. The cause of this is the strong crystal field acting on defects as in gadolinium impurities and on gadolinium oxide nanoparticles and gadolinium defects in semiconductors in contrast to bulk gadolinium oxide . The calculation of the contribution of spin‐orbit coupling to the energetics of the gadolinium oxide clusters evidence that this contribution is below 1 meV and this computationally costly part of the calculations can be omitted in considered case.…”