A theoretical investigation on the Cr ð H 2 O Þ 0 ; 1 C n ð n Z 1 – 4 Þ clusters by density functional theory methods

The first systematic study of the CrðH2OÞ n ðnZ1K4Þ series of clusters is herein presented at the level of the unrestricted DFT B3LYP level in conjunction with electron core potential basis sets. The present structures are relevant for laser-induced and laser-ablation syntheses of chromium compounds, and also for fundamental spectroscopy studies of metal-bearing species in the gas phase. Calculated properties include optimal geometries, total energies, bond lengths, bond angles, natural orbital analysis charges, hydration dissociation energies, and HOMO– LUMO gaps inter alia. Present results reveal a strict correlation between the clusters total energy and their spin state. Except for CrðH2OÞ 4 , the most stable clusters in each CrðH2OÞ n ðnZ1–4Þ series are high-spin states. Comparisons with a few available theoretical results show good agreement. q 2005 Elsevier B.V. All rights reserved.