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Ab Initio Calculations on the Electronically Excited States of Small Helium Clusters

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Department of Chemistry, University of California at Berkeley, and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720
* To whom correspondence should be addressed. E-mail: [email protected]
†University of California at Berkeley.
‡Lawrence Berkeley National Laboratory.
Cite this: J. Phys. Chem. A 2010, 114, 31, 8023–8032
Publication Date (Web):July 15, 2010
https://doi.org/10.1021/jp103532q
Copyright © 2010 American Chemical Society
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Abstract

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The vertical excitation energies of small helium clusters, He7 and He25, have been calculated using configuration interaction singles, and the character of the excited states was determined using attachment/detachment density analysis. It was found that in the n = 2 manifold the excitations could be interpreted as superpositions of atomic states, with excitations on the surface of the clusters being lower in energy than those in the bulk. For the n = 2 excited states with significant density on the interior of the cluster, mixing with the atomic n = 3 states resulted in lower excitation energies. For the n = 3 states the spatial extent of the excited-state density can be much larger than the size of the cluster, making analysis of the states more difficult and highly dependent on the internuclear distance. Introducing disorder into the clusters results in some localization of the excited states, although highly delocalized states are always observed in these small clusters. In addition, experimental results for small clusters are interpreted in terms of these findings.

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