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Author Farrelly, D. ♦ Iñarrea, M. ♦ Salas, J. P. ♦ Lanchares, V.
Source United States Department of Energy Office of Scientific and Technical Information
Content type Text
Language English
Subject Keyword INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ♦ CALCULATION METHODS ♦ COMPUTERIZED SIMULATION ♦ DECOUPLING ♦ DOPED MATERIALS ♦ HELIUM 4 ♦ MOLECULAR CLUSTERS ♦ MOLECULES ♦ QUANTUM MECHANICS ♦ SOLVATION ♦ SOLVENTS
Abstract Small {sup 4}He clusters doped with various molecules allow for the study of “quantum solvation” as a function of cluster size. A peculiarity of quantum solvation is that, as the number of {sup 4}He atoms is increased from N = 1, the solvent appears to decouple from the molecule which, in turn, appears to undergo free rotation. This is generally taken to signify the onset of “microscopic superfluidity.” Currently, little is known about the quantum mechanics of the decoupling mechanism, mainly because the system is a quantum (N + 1)-body problem in three dimensions which makes computations difficult. Here, a one-dimensional model is studied in which the {sup 4}He atoms are confined to revolve on a ring and encircle a rotating CO molecule. The Lanczos algorithm is used to investigate the eigenvalue spectrum as the number of {sup 4}He atoms is varied. Substantial solvent decoupling is observed for as few as N = 5 {sup 4}He atoms. Examination of the Hamiltonian matrix, which has an almost block diagonal structure, reveals increasingly weak inter-block (solvent-molecule) coupling as the number of {sup 4}He atoms is increased. In the absence of a dopant molecule the system is similar to a Lieb-Liniger (LL) gas and we find a relatively rapid transition to the LL limit as N is increased. In essence, the molecule initially—for very small N—provides a central, if relatively weak, attraction to organize the cluster; as more {sup 4}He atoms are added, the repulsive interactions between the identical bosons start to dominate as the solvation ring (shell) becomes more crowded which causes the molecule to start to decouple. For low N, the molecule pins the atoms in place relative to itself; as N increases the atom-atom repulsion starts to dominate the Hamiltonian and the molecule decouples. We conclude that, while the notion of superfluidity is a useful and correct description of the decoupling process, a molecular viewpoint provides complementary insights into the quantum mechanism of the transition from a molecular cluster to a quantum solvated molecule.
ISSN 00219606
Educational Use Research
Learning Resource Type Article
Publisher Date 2016-05-28
Publisher Place United States
Journal Journal of Chemical Physics
Volume Number 144
Issue Number 20


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