Ab initio calculations for the photoelectron spectra of vanadium clusters.
We report ab initio calculations for the electronic and structural properties of V(n), V(n) (-), and V(n) (+) clusters up to n=8. We performed the calculations using a real-space pseudopotential method based on the local spin density approximation for exchange and correlation. This method assumes no explicit basis. Wave functions are evaluated on a uniform grid; only one parameter, the grid spacing, is used to control convergence of the electronic properties. Charged states are easily handled in real space, in contrast to methods based on supercells where Coulombic divergences require special handling. For each size and charge state, we find the lowest energy structure. Our results for the photoelectron spectra, using the optimized structure, agree well with those obtained by experiment. We also obtain satisfactory agreement with the measured ionization potential and electron affinity, and compare our results to calculations using an explicit basis.
Li
Shen
S
Department of Chemical Engineering and Materials Science, Institute for the Theory of Advanced Materials in Information Technology, Digital Technology Center, University of Minnesota, Minneapolis, Minnesota 55455, USA.
Alemany
M M G
MM
Chelikowsky
James R
JR