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Unraveling the internal dynamics of the benzene dimer: a combined theoretical and microwave spectroscopy study

MPS-Authors
http://pubman.mpdl.mpg.de/cone/persons/resource/persons21495

Erlekam,  Undine
Molecular Physics, Fritz Haber Institute, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons39203

Bunker,  Phil
Molecular Physics, Fritz Haber Institute, Max Planck Society;
National Research Council of Canada;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons21614

Helden,  Gert von
Molecular Physics, Fritz Haber Institute, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons21859

Meijer,  Gerard
Molecular Physics, Fritz Haber Institute, Max Planck Society;

Avoird ,  Ad van der
Molecular Physics, Fritz Haber Institute, Max Planck Society;
Theoretical Chemistry, Institute for Molecules and Materials, Radboud University Nijmegen;

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Citation

Schnell, M., Erlekam, U., Bunker, P., Helden, G. v., Grabow, J.-U., Meijer, G., et al. (2013). Unraveling the internal dynamics of the benzene dimer: a combined theoretical and microwave spectroscopy study. Physical Chemistry Chemical Physics, 15(25), 10207-10223. doi:10.1039/c3cp51181b.


Cite as: http://hdl.handle.net/11858/00-001M-0000-0013-FAEE-2
Abstract
We report a combined theoretical and microwave spectroscopy study of the internal dynamics of the benzene dimer, a benchmark system for dispersion forces. Although the extensive ab initio calculations and experimental work on the equilibrium geometry of this dimer have converged to a tilted T-shaped structure, the rich internal dynamics due to low barriers for internal rotation have remained largely unexplored. We present new microwave spectroscopy data for both the normal (C6H6)2 and partially deuterated (C6D6)(C6H6) dimers. The splitting patterns obtained for both species are unraveled and understood using a reduced-dimensionality theoretical approach. The hindered sixfold rotation of the stem can explain the observed characteristic 1 : 2 : 1 tunneling splitting pattern, but only the concerted stem rotation and tilt tunneling motion, accompanied by overall rotation of the dimer, yield the correct magnitude of the splittings and their strong dependence on the dimer angular momentum J that is essential to explain the experimental data. Also the surprising observation that the splittings are reduced by 30% for the mixed (C6D6)C(C6H6)S dimer in which only the cap (C) in the T-shaped structure is deuterated, while the rotating stem (S) monomer is the same as in the homodimer, is understood using this approach. Stark shift measurements allowed us to determine the dipole moment of the benzene dimer, μ = 0.58 ± 0.051 D. The assumption that this dipole moment is the vector sum of the dipole moments induced in the monomers by the electric field of the quadrupole on the other monomer yields a calculated value of μ = 0.63 D. Furthermore, the observed Stark behavior is typical for a symmetric top, another confirmation of our analysis.