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Blueshift and intramolecular tunneling of NH3 umbrella mode in 4Hen clusters

J. Chem. Phys. 127, 194303 (2007); doi:10.1063/1.2787004

Published 16 November 2007

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Alexandra Viel
Kenneth S. Pitzer Center for Theoretical Chemistry, Department of Chemistry, University of California, Berkeley, California 94720-1460, USA and Laboratoire de Physique des Atomes, Lasers, Molécules et Surfaces (PALMS), UMR 6627 du CNRS, Université de Rennes 1, Campus de Beaulieu, F-35042 Rennes, France

K. Birgitta Whaley
Kenneth S. Pitzer Center for Theoretical Chemistry, Department of Chemistry, University of California, Berkeley, California 94720-1460, USA

Richard J. Wheatley
School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, United Kingdom
We present diffusion Monte Carlo calculations of the ground and first excited vibrational states of NH3  4Hen for n<=40. We use the potential energy surface developed by one of us [M. P. Hodges and R. J. Wheatley, J. Chem. Phys. 114, 8836 (2001)], which includes the umbrella mode coordinate of NH3. Using quantum Monte Carlo calculations of excited states, we show that this potential is able to reproduce qualitatively the experimentally observed effects of the helium environment, namely, a blueshift of the umbrella mode frequency and a reduction of the tunneling splittings in ground and first excited vibrational states of the molecule. These basic features are found to result regardless of whether dynamical approximations or exact calculations are employed. ©2007 American Institute of Physics
History: Received 15 May 2006; accepted 28 August 2007; published 16 November 2007
Permalink: http://link.aip.org/link/?JCPSA6/127/194303/1
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KEYWORDS and PACS

Keywords
PACS
  • 36.40.Sx
    Diffusion and dynamics of atomic and molecular clusters
  • 31.50.-x
    Potential energy surfaces (atoms and molecules)
  • 34.30.+h
    Intramolecular energy transfer; intramolecular dynamics; dynamics of van der Waals molecules
  • 33.70.Jg
    Molecular line and band widths, shapes, and shifts
  • YEAR: 2007

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PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
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REFERENCES (45)
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