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  Stark Effect in the Benzene Dimer

Schnell, M., Bunker, P., Helden, G. v., Grabow, J.-U., Meijer, G., & van der Avoird, A. (2013). Stark Effect in the Benzene Dimer. The Journal of Physical Chemistry A, 117(50), 13775-13778. doi:10.1021/jp408076q.

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Item Permalink: http://hdl.handle.net/11858/00-001M-0000-0024-B9CC-D Version Permalink: http://hdl.handle.net/11858/00-001M-0000-0024-B9D0-1
Genre: Journal Article

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https://dx.doi.org/10.1021/jp408076q (Publisher version)
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 Creators:
Schnell, Melanie1, 2, Author              
Bunker, Phil3, 4, Author              
Helden, Gert von4, Author              
Grabow, Jens-Uwe5, Author
Meijer, Gerard4, 6, Author              
van der Avoird, Ad6, Author
Affiliations:
1Structure and Dynamics of Cold and Controlled Molecules, Independent Research Groups, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society, ou_1938292              
2Center for Free-Electron Laser Science, Notkestrasse 85, 22607 Hamburg, Germany, ou_persistent22              
3Steacie Laboratory, National Research Council of Canada, Ottawa, Ontario K1A0R6, Canada, ou_persistent22              
4Molecular Physics, Fritz Haber Institute, Max Planck Society, ou_634545              
5Institut für Physikalische Chemie und Elektrochemie, Gottfried Wilhelm Leibniz Universität Hannover, Callinstrasse 3A, D-30167 Hannover, Germany, ou_persistent22              
6Theoretical Chemistry, Institute for Molecules and Materials, Radboud University Nijmegen, Heyendaalseweg 135, 6525 AJ Nijmegen, The Netherlands, ou_persistent22              

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 Abstract: Ab initio calculations of the six-dimensional intermolecular potential have shown the benzene dimer to be an asymmetric top molecule at equilibrium with one benzene moiety forming the “stem” and the other a “tilted cap” in a T-shaped structure. Internal rotation of the cap about its C6 axis is essentially free; the barriers for cap tilting and for internal rotation of the stem about its C6 axis are hindered by successively higher barriers. In previous work we have validated these theoretical results using Fourier transform microwave spectroscopy in conjunction with dynamics calculations. We have also measured the Stark effect, and despite the fact that the equilibrium structure is that of an asymmetric top, the assigned transitions involving K = 0 exhibit a second-order Stark effect whereas those involving K = 1 exhibit a first-order Stark effect. This is typical for a symmetric-top molecule, but anomalous for an asymmetric-top molecule. We use symmetry arguments to explain how this asymmetric-top molecule can have a first-order Stark effect in certain states that have excitation of cap internal rotation. Cap internal rotation is essentially the twisting of the monomers relative to each other about the intermolecular axis, and such torsional motion occurs in other asymmetric top dimers such as benzene–CO and benzene–H2O. These latter dimers will also have levels that exhibit a first-order Stark effect, which we can explain using our symmetry arguments.

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Language(s): eng - English
 Dates: 2013-09-192013-08-122013-09-192013-09-192013-12-19
 Publication Status: Published in print
 Pages: 4
 Publishing info: -
 Table of Contents: -
 Rev. Method: Peer
 Identifiers: DOI: 10.1021/jp408076q
 Degree: -

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Title: The Journal of Physical Chemistry A
  Other : J. Phys. Chem. A
Source Genre: Journal
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Publ. Info: Columbus, OH : American Chemical Society
Pages: - Volume / Issue: 117 (50) Sequence Number: - Start / End Page: 13775 - 13778 Identifier: ISSN: 1089-5639
CoNE: https://pure.mpg.de/cone/journals/resource/954926947766_4