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Rotational spectrum of cyanoacetylene solvated with helium atoms

J. Chem. Phys. 125, 144310 (2006); doi:10.1063/1.2357604

Published 10 October 2006

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W. Topic, W. Jäger, N. Blinov, and P.-N. Roy
Department of Chemistry, University of Alberta, Edmonton, Alberta T6G 2G2, Canada

M. Botti
CASPUR-Via dei Tizii 6/b,- I-00185 Roma, Italy

S. Moroni
INFM-DEMOCRITOS National Simulation Center, and SISSA, via Beirut 2-4, I-34014 Trieste, Italy
The high resolution microwave spectra of HeN–HCCCN clusters were studied in the size ranges of 1–18 and 25–31. In the absence of an accompanying infrared study, rotational excitation energies were computed by the reptation quantum Monte Carlo method and used to facilitate the search and assignment of R(0) transitions from N>6, as well as R(1) transitions with N>1. The assignments in the range of 25–31 are accurate to ±2 cluster size units, with an essentially certain relative ordering. The rotational transition frequencies decrease with N=1–6 and then show oscillatory behavior for larger cluster sizes, which is now recognized to be a manifestation of the onset and microscopic evolution of superfluidity. For cluster sizes beyond completion of the first solvation shell the rotational frequencies increase significantly above the large-droplet limit. This behavior, common to other linear molecules whose interaction with He features a strong nearly equatorial minimum, is analyzed using path integral Monte Carlo simulations. The He density in the incipient second solvation shell is shown to open a new channel for long permutation cycles, thus increasing the decoupling of the quantum solvent from the rotation of the dopant molecule. ©2006 American Institute of Physics
History: Received 11 August 2006; accepted 29 August 2006; published 10 October 2006
Permalink: http://link.aip.org/link/?JCPSA6/125/144310/1
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Supplemental Material

KEYWORDS and PACS

Keywords
PACS
  • 36.40.Mr
    Spectroscopy and geometrical structure of atomic and molecular clusters
  • 33.15.Mt
    Molecular rotation, vibration, and vibration-rotation constants
  • 33.20.Bx
    Radio-frequency and microwave molecular spectra
  • 33.20.Sn
    Rotational analysis (molecular spectra)
  • YEAR: 2006

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PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
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REFERENCES (36)
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