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Thermodynamics of atomic clusters using variational quantum hydrodynamics.

Derrickson SW, Bittner ER

Department of Chemistry and Center for Materials Chemistry, University of Houston, Houston, Texas 77204, USA.

Small clusters of rare-gas atoms are ideal test cases for studying how quantum delocalization affects both the thermodynamics and the structure of molecular scale systems. In this paper, we use a variational quantum hydrodynamic approach to examine the structure and dynamics of (Ne)n clusters, with n up to 100 atoms, at both T = 0 K and for temperatures spanning the solid-to-liquid transition in bulk Ne. Finite temperature contributions are introduced to the grand potential in the form of an "entropy" potential. One surprising result is the prediction of a negative heat capacity for very small clusters that we attribute to the nonadditive nature of the total free-energy for very small systems.

Published 11 October 2007 in J Phys Chem A, 111(41): 10345-52.
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