scattering study of 11 tetramethylpyrazine chloranilic英文资料.pdfVIP

THE JOURNAL OF CHEMICAL PHYSICS 125, 194525 2006 X-ray diffraction and inelastic neutron scattering study of 1:1 tetramethylpyrazine chloranilic acid complex: temperature, isotope, and pressure effects M. Pragera,b Institut für Festkörperforschung, Forschungszentrum Jülich, 52425 Jülich, Germany A. Pietraszko Institute of Low Temperature and Structure Research, Polish Academy of Sciences, ulica Okolna, 50-950 Wroclaw, Poland L. Sobczyka Faculty of Chemistry, University of Wroclaw, Joliot-Curie 14, 50-383 Wroclaw, Poland A. Pawlukojć Institute of Nuclear Chemistry and Technology, ulica Dorodna 16, 03-195 Warsaw, Poland E. Grech Institute of Chemistry and Environmental Protection, Szczecin University of Technology, Piastów Aleja 12, 71-065 Szczecin, Poland T. Seydel Institut Laue Langevin, 38042 Grenoble, France A. Wischnewski and M. Zamponi Institut für Festkörperforschung, Forschungszentrum Jülich, 52425 Jülich, Germany Received 29 June 2006; accepted 6 September 2006; published online 21 November 2006 The x-ray diffraction studies of the title complex were carried out at room temperature and 14 K for H/D in hydrogen bridge isotopomers. At 82 K a phase transition takes place leading to a doubling of unit cells and alternation of the hydrogen bond lengths linking tetramethylpyrazine TMP and chloranilic acid molecules. A marked H/D isotope effect on these lengths was found at room temperature. The elongation is much smaller at 14 K. The infrared isotopic ratio for O–HD¯N bands equals to 1.33. The four tunnel splittings of methyl librational ground states of the protonated complex required by the structure are determined at a temperatur