Systematic theoretical investigation of structure and electronic properties of pure copper and lithium doped copper clusters

The pure copper and lithium-doped copper clusters are studied using the unbiased CALYPSO structure searching method and density function theory to understand the evolution of various structure and electronic properties. Theoretical results show the growth behaviours of doped clusters are organised as follows: Li capped Cu-n clusters or Li substituted Cun+1 clusters as well as Cu capped Cun-1Li clusters. Moreover, the lowest energy structures of CunLi favour planar structures for n <= 3 and three-dimensional structures for n = 4-12. In addition, the calculated averaged binding energies, fragmentation energies and second-order difference of energies exhibit obvious odd-even alternations as cluster size increasing. At last, the highest occupied-lowest unoccupied molecular orbital gaps, molecular orbital energy, magnetic property, natural population analysis, natural electron configurations, electrostatic potential, electron density difference, Infrared and Raman spectra and density of states are also, respectively, operative for characterising and rationalising the electronic properties of doped clusters. [GRAPHICS] .