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dc.creatorSchnell, Melanieen_US
dc.creatorErlekam, Undineen_US
dc.creatorVon Helden, Gerten_US
dc.creatorMeijer, Gerarden_US
dc.creatorBunker, Philip R.en_US
dc.creatorGrabow, Jens-Uween_US
dc.creatorVan Der Avoird, Aden_US
dc.date.accessioned2013-07-16T21:34:04Z
dc.date.available2013-07-16T21:34:04Z
dc.date.issued2013en_US
dc.identifier2013-FB-10en_US
dc.identifier.urihttp://hdl.handle.net/1811/55204
dc.descriptionAuthor Institution: Center for Free-Electron Laser Science, 22761 Hamburg, Germany; Max-Planck-Institut fur Kernphysik, 69117 Heidelberg, Germany; Fritz-Haber-Institut der Max-Planck-Gesellschaft, 14195 Berlin, Germany; National Research Council of Canada, Ottawa, Ontario K1A 0R6, Canada; Institut fur Physikalische Chemie und Elektrochemie, Gottfried-Wilhelm-Leibniz-Universtat, 30167 Hannover, Germany; Institute for Molecules and Materials, Radboud University, 6525 AJ Nijmegen, The Netherlandsen_US
dc.description.abstractThe benzene dimer is the prototype system for Van der Waals interactions between aromatic molecules. Here, we report a joint experimental and theoretical study regarding normal (C$_6$H$_6$)$_2$ and the partially deuterated (C$_6$D$_6$)(C$_6$H$_6$) isotopologue. Interestingly, although its tilted T-shaped equilibrium structure corresponds to an asymmetric rotor, both isotopologues exhibit the rotational spectrum of a symmetric rotor, with a characteristic quartet splitting pattern due to internal tunneling motions: each transition exhibits a $-2 : -1 : +1 : +2$ splitting ratio with respect to its center. We unravel these splittings with the aid of the unrivalled resolution of the supersonic-jet FT-microwave experiment which provides accurate split-patterns, by means of a reduced-dimensionality model for the internal dynamics of the (rotating) dimer that reproduces them. They turn out to originate from a concerted tunneling mechanism involving both the hindered rotation of the stem in the T-shaped dimer around its sixfold axis and tilt tunneling. We also show that the observed intensities of the tunneling components are not solely determined by nuclear spin statistical weights. Rather, taking small differences in the dissociation energies of different dimer nuclear spin species into account, the kinetics of the dimer formation and equilibration can bias the populations of the tunneling symmetry species. Using Stark shift measurements, we determine the dipole moment of (C$_6$H$_6$)$_2$ to be $\mu$ = 0.580(51) D, in agreement with the value of 0.63 D calculated with the assumption that the dipole moment is mainly determined by the dipoles induced in both monomers by the electric field of the quadrupole of the other monomer.en_US
dc.language.isoenen_US
dc.publisherOhio State Universityen_US
dc.titleSTRUCTURE OF THE BENZENE DIMER---GOVERNED BY DYNAMICSen_US
dc.typeArticleen_US
dc.typeImageen_US
dc.typePresentationen_US


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