Divergent interpretations have appeared in the literature regarding the structural nature and evolutionary behavior for photoluminescent CdSe nanospecies with sharp doublets in optical absorption. We report a comprehensive description of the transformation pathway from one CdSe nanospecies displaying an absorption doublet at 373/393 nm to another species with a doublet at 433/460 nm. These two nanospecies are zero‐dimensional (0D) magic‐size clusters (MSCs) with 3D quantum confinement, and are labeled dMSC‐393 and dMSC‐460, respectively. Synchrotron‐based small‐angle X‐ray scattering (SAXS) returns a radius of gyration of 0.92 nm for dMSC‐393 and 1.14 nm for dMSC‐460, and indicates that both types are disc shaped with the exponent of the SAXS form factor equal to 2.1. The MSCs develop from their unique counterpart precursor compounds (PCs), which are labeled PC‐393 and PC‐460, respectively. For the dMSC‐393 to dMSC‐460 transformation, the proposed PC‐enabled pathway is comprised of three key steps, dMSC‐393 to PC‐393 (Step 1), PC‐393 to PC‐460 (Step 2 involving monomer addition), and PC‐460 to dMSC‐460 (Step 3). The present study provides a framework for understanding the PC‐based evolution of MSCs and how PCs enable transformations between MSCs.

The structural, electronic, and magnetic properties of iridium clusters with sizes of n = 2-15 are investigated by employing the generalized gradient approximation of density functional theory. Simple cube evolution pattern is revealed for Ir(2-15) clusters, as predicted by previous reports. It is remarkable that for Ir(10), Ir(11) clusters, new generated isomers with higher stabilities relative to those reported in previous studies are obtained. The even-sized clusters are more stable than the odd-sized species. The Ir-Ir bonds in the cubic Ir(8) and Ir(12) clusters, which are considered as the basic units in the structural evolution present covalent character. Starting from n = 8, the magnetic moments of Ir(n) clusters decrease sharply. The moments of magnetic clusters show 5d characters. The reactive site selectivity of studied clusters with n = 5-15 is analyzed with condensed Fukui function. The capped atoms in certain clusters (Ir(9), Ir(10), Ir(11), and Ir(13)) generally show extraordinary activity for both nucleophilic and electrophilic attack.

Equilibrium geometries of AlnTi (n = 2-24) clusters were studied using density-functional theory with generalized gradient approximation. The resulting geometries showed that the titanium atom remains on the surface of clusters for n < 20 but is endohedrally doped from n = 20. This structural transition confirms the previous experiment results obtained by studying their abilities for argon physisorption (Lang, S. M.; Claes, P.; Neukermans, S.; Janssens, E. J. Am. Soc. Mass Spectrom.2011, 22, 1508). The average bond lengths, coordination numbers, relative stabilities, electronic properties, and other relevant properties were discussed. It was found that the doped titanium atoms strengthen the stabilities of the pure aluminum clusters. The coordination numbers of titanium atoms along with the average Al-Ti bond lengths undergo dramatic increases during the structural transition. The intra-atomic hybridization exists in both Ti and Al atoms, and charge transfer from Al atoms to Ti atom were found in these complexes, which should reflect the strength of Al-Ti interactions. Electronic structure analysis based on the partial density of states reveals stronger Al-Ti interactions for the endohedrally doped structures.

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