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

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dc.identifier.uri http://dx.doi.org/10.15488/147
dc.identifier.uri http://www.repo.uni-hannover.de/handle/123456789/165
dc.contributor.author Schnell, Melanie ger
dc.contributor.author Erlekam, Undine ger
dc.contributor.author Bunker, P. R ger
dc.contributor.author Helden, Gert von ger
dc.contributor.author Grabow, Jens-Uwe ger
dc.contributor.author Meijer, Gerard ger
dc.contributor.author Avoird, Ad van der ger
dc.date.accessioned 2015-12-08T16:07:31Z
dc.date.available 2015-12-08T16:07:31Z
dc.date.issued 2013-05-16
dc.identifier.citation Schnell, Melanie; Erlekam, Undine; Bunker, P. R.; Helden, Gert von; Grabow, Jens-Uwe; Meijer, Gerard; Avoird, Ad van der: Unraveling the internal dynamics of the benzene dimer: a combined theoretical and microwave spectroscopy study. In: Physical Chemistry Chemical Physics 15 (2013), Nr. 25, S. 10207-10223. DOI: http://dx.doi.org/10.1039/c3cp51181b
dc.description.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, mu = 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 mu = 0.63 D. Furthermore, the observed Stark behavior is typical for a symmetric top, another confirmation of our analysis. ger
dc.description.sponsorship Chemische Industrie
dc.description.sponsorship DFG
dc.description.sponsorship Land Niedersachsen
dc.language.iso eng eng
dc.publisher Cambridge : Royal Society of Chemistry
dc.relation.ispartofseries Physical Chemistry Chemical Physics 15 (2013), Nr. 25
dc.rights CC BY 3.0
dc.rights.uri http://creativecommons.org/licenses/by/3.0/
dc.subject rotation-tunneling states eng
dc.subject coupled 6-dimensional calculations eng
dc.subject discrete variable representation eng
dc.subject potential-energy surface eng
dc.subject matrix kohn method eng
dc.subject water dimer eng
dc.subject resonance spectroscopy eng
dc.subject aromatic interactions eng
dc.subject stacking interactions eng
dc.subject reactive scattering eng
dc.subject.ddc 540 | Chemie ger
dc.subject.ddc 530 | Physik ger
dc.title Unraveling the internal dynamics of the benzene dimer: a combined theoretical and microwave spectroscopy study eng
dc.type article
dc.type Text
dc.relation.issn 1463-9076
dc.relation.doi http://dx.doi.org/10.1039/c3cp51181b
dc.bibliographicCitation.issue 25
dc.bibliographicCitation.volume 15
dc.bibliographicCitation.date 2013
dc.bibliographicCitation.firstPage 10207
dc.bibliographicCitation.lastPage 10223
dc.description.version publishedVersion
tib.accessRights frei zug�nglich


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