Theoretical investigations on geometrical and electronic structures of silver clusters

Geometrical structures and ground and excited states of silver clusters are theoretically investigated using long-range corrected (LC) density functional theory (DFT) calculations. The discrepancy between HOMO-LUMO gaps and the vertical ionization potential minus vertical electron affinity values, which should be the same values, is explored to reveal the significance of long-range exchange effects on the electronic states of metal clusters. The difference between HOMO-LUMO gaps and HOMO-LUMO excitation energies, which is called "exciton binding energy," is also tested. As a result, it is found that the long-range exchange effects are requisite in DFT calculations to quantitatively investigate the ground and excited states of metal clusters. © 2018 Wiley Periodicals, Inc.