Structural Growth Pattern, Electronic Configurations, and Spectral and Thermochemistry Properties of ZrSn ( = 4-17) Nanoscale Compounds: A Systematic Study Using Density Functional Theory.

By performing density functional theory (DFT) calculations for geometric optimization in conjunction with the artificial bee colony algorithm for cluster (ABCluster) global search approach, the ground-state structures of the neutral, anionic, and dianionic ZrSn ( = 4-17) nanoscale compounds are obtained. Their structural growth evolution, spectral information, and electronic and thermochemical properties are investigated. Regarding the architectural evolution of the neutral, anion, and dianionic species, ZrSn ( = 4-17) compounds possess two different stages of adsorption patterns in which, when = 4-7 and = 8-17, ZrSn and ZrSn compounds as the basic motif adsorb Sn atoms to become the larger clusters, respectively. The simulated photoelectron spectra (PES) of anionic compounds are in good agreement with the available experimental PES. The infrared and Raman spectra can be summarized as follows: under infrared vibrational modes, the sealed cages of ZrSn compounds belong to the deformation mode, and under Raman vibrational modes, they belong to the breathing mode of the Sn cage framework. The density of states (DOS) spectra and natural population analysis (NPA) indicate that the interaction between the Zr atom and Sn frameworks of capsulated compounds has been developing stronger than for unsealed compounds. The results of thermochemical properties, molecular orbital shell (MOs) analysis, and ultraviolet-visible (UV-vis) absorption spectrum indicate that the neutral ZrSn nanoscale compound possesses not only both thermodynamic and chemical stability but also far-infrared sensing and optoelectronic properties and hence, is the best building block motif for new multipurpose nanoscale materials.