Structural evolution and electronic properties of medium-sized CrSin−/0 (n = 19–25) clusters.

Herein, the structural evolution, electronic and magnetic properties of CrSin−/0 for n = 19–25 have been investigated at density functional theory (DFT) level. The global minimum structures of these clusters have been fully searched through a self-developed genetic algorithm code combined with DFT calculations. Both of anionic and neutral CrSin for n = 19–25 share the same configurations. All these clusters prefer to adopt endohedral structures (Cr@Si14 for sizes n = 19–21, and Cr@Si13 for larger ones) as the structural motif with the remaining Si atoms attached on the surface. Among all these clusters, CrSi22 and CrSi23 are the most prominent through the analysis of HOMO − LUMO gaps, average binding energies, and the second order of energy differences. All of these medium-sized cluster anions possess the same total magnetic moment of 1 μB, but with very different contributions from that of small sizes (n ≤ 18), except for size 22. [ABSTRACT FROM AUTHOR]