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          Institute: MPI für medizinische Forschung     Collection: Forschungsgruppe Prof. Dr. Haeberlen     Display Documents



ID: 22940.0, MPI für medizinische Forschung / Forschungsgruppe Prof. Dr. Haeberlen
Quantification of the Orientational Disorder in ortho-dichlorotetramethylbenzene. A single Crystal Deuterium NMR and X-ray Diffraction Study of the Site Populations
Translation of Title:Quantification of the Orientational Disorder in ortho-dichlorotetramethylbenzene. A single Crystal Deuterium NMR and X-ray Diffraction Study of the Site Populations
Authors:Bräuninger, Thomas; Poupko, Raphy; Zimmermann, Herbert; Luz, Zeev; Haeberlen, Ulrich
Language:English
Date of Publication (YYYY-MM-DD):2001-11
Title of Journal:Journal of Chemical Physics
Journal Abbrev.:J. Chem. Phys.
Volume:115
Issue / Number:17
Start Page:8049
End Page:8059
Review Status:Peer-review
Audience:Experts Only
Intended Educational Use:No
Abstract / Description:The title compound, 1,2-dichloro-3,4,5,6-tetramethylbenzene (DCTMB) exhibits three solid phases, III, II, and I, of which two, Phase III (<170 K) and Phase II (170–381 K), have been investigated in the present study by means of x-ray diffraction and deuterium NMR. The latter measurements were performed on powder and single crystal samples of perdeuterated DCTMB (DCTMB-d12). Phase III is right–left disordered, with the molecular para axes (the axes having two methyls in para positions) well ordered in the crystal. The right–left disorder is manifested by the fact that the chlorine and ortho methyls have each an occupancy number of &frac12;, thus ensuring an average inversion symmetry at the molecular site. The NMR results also indicate that at least one of the ortho methyls, and probably the second one too, are slightly distorted, randomly up and down, relative to the benzene plane. Except for fast methyl group rotation the molecules in this phase are static on the NMR time scale. Phase II is much more mobile and disordered, with the molecular para axes distributed over all six local crystallographic orientations. A detailed analysis of the single crystal NMR results shows that the fractional populations in the various orientations are biased with some orientations more populated than others (while keeping average inversion symmetry). It is shown that this bias is due to differences in both the enthalpy and entropy associated with the various orientations. NMR line shape and T1 relaxation data in Phase II (and I) indicate rapid jumps between the different orientations in the high temperature range of the measurements. The estimated activation parameters for the reorientational jumps are E&alpha; = 33 kJ/mol and k(260 K) = 4.5×107 s–1.
External Publication Status:published
Document Type:Article
Communicated by:Wulf Kaiser
Affiliations:MPI für medizinische Forschung/Abteilung Biophysik/
MPI für medizinische Forschung/Forschungsgruppe Molekülkristalle/
Identifiers:URI:http://ojps.aip.org/journals/doc/JCPSA6-ft/vol_115... [Full text]
URI:http://ojps.aip.org/getabs/servlet/GetabsServlet?p... [Abstract]
URI:http://ojps.aip.org/getpdf/servlet/GetPDFServlet?f... [Fulltext PDF]
DOI:10.1063/1.1407840
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