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Summary: Structure and energetics of He2* bubble-states in superfluid 4
He
J. Eloranta, N. Schwentner,a)
and V. A. Apkarian
Department of Chemistry, University of California, Irvine, California 92697-2025
Received 8 October 2001; accepted 11 December 2001
Structure and energetics of solvation of the triplet Rydberg states of the He2* excimer in liquid 4
He
LHe are analyzed using ab initio potentials and density functional methods. The results are used
to interpret the known spectroscopy. Having established the reliability of the various semiempirical
functionals, interfacial properties of the superfluid on molecular scales are discussed. Due to its
spherical electron density, the a(3
u) state solvates in a spherical bubble of 7 Å radius in which the
excimer freely rotates. This explains the observed rotationally resolved 3
b3
a and 3
c3
a
absorption spectra. A deep potential minimum occurs at the equatorial node of the c(3
u) state,
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