Molecular Reorientation in the Plastic Crystalline Phase of Tris

1979 ◽  
Vol 32 (4) ◽  
pp. 905 ◽  
Author(s):  
RE Wasylishen ◽  
PF Barron ◽  
DM Doddrell
Keyword(s):  
Phase Transition ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Spin Lattice Relaxation ◽  
X Ray Diffraction ◽  
Scanning Calorimetry ◽  
Molecular Reorientation ◽  
Liquid Phase Transition ◽  
X Ray ◽  
Spin Lattice

Carbon-13 N.M.R. spectra of tris(hydroxymethyl)aminomethane (Tris) have been measured between 407 and 461 K. Proton-decoupled 13C N.M.R. spectra of solid Tris between 407 K and its melting point are relatively sharp (v� < 30 Hz) indicating rapid overall molecular reorientation in this temperature range. It was not possible to detect a 13C N.M.R, signal for Tris below 407 K. The observed 13C N.M.R. spin-lattice relaxation times appear continuous across the solid ↔ liquid phase transition. From the temperature dependence of T1, a rotational activation energy of 51.6 � 6 kJ mol-1 is calculated, which indicates that the molecules must expend considerable energy in reorienting. The N.M.R. results are discussed in relation to previous differential scanning calorimetry and X-ray diffraction data which indicate that Tris undergoes a solid ↔ solid transition at 407 K.

Molecular Motions in Halogen-Bridged One-Dimensional Pt Complexes, [PtII(en)2][PtIVX2(en)2](ClO4)4 (X = Cl, Br) Studied by 2H and 1H NMR

2002 ◽  
Vol 57 (6-7) ◽  
pp. 413-418 ◽  
Author(s):  
Noriyoshi Kimura ◽  
Toru Hachisuka ◽  
Yukitaka Nakano ◽  
Ryuichi Ikeda
Keyword(s):  
Relaxation Times ◽  
Lattice Relaxation ◽  
Energy Difference ◽  
Spin Lattice Relaxation ◽  
X Ray Diffraction ◽  
Potential Wells ◽  
One Dimensional ◽  
X Ray ◽  
Spin Lattice ◽  
H Nmr

2H and 1H NMR measurements were performed on crystalline [Pt(en)2][PtX2(en)2](ClO4)4 (X = Cl, Br), where the protonated and partially deuterated ethylenediamines (en’s), NH2(CH2)2NH2, NH2(CD2)2NH2 and ND2(CH2)2ND2 were used as ligands. Measurements of 2H and 1H NMR spin-lattice relaxation times showed the presence of motions of en chelate rings at the temperatures near the phase transitions, whereas broad 2H NMR spectra and the reported X-ray diffraction data showed no marked motions. These results were consistently explained by introducing the en puckering motion between highly asymmetric potential wells with an energy difference of 10 - 13 kJ mol-1. This difference was shown to be much larger than 2 - 5 kJ mol-1, reported for the iodo-complex, [Pt(en)2][PtI2(en)2](ClO4)4

A study of molecular motion in tetramethylphosphonium halides by proton magnetic resonance

1976 ◽  
Vol 54 (12) ◽  
pp. 1985-1990 ◽  
Author(s):  
T. T. Ang ◽  
B. A. Dunell
Keyword(s):  
Molecular Motion ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Spin Lattice Relaxation ◽  
X Ray Diffraction ◽  
Hexagonal Crystal ◽  
Methyl Group ◽  
X Ray ◽  
Spin Lattice ◽  
Second Moments

Spin–lattice relaxation times of tetramethylphosphonium chloride, bromide, and iodide were measured between 100 and 500 K and the two minima in T1 found for each compound have been assigned to methyl group reorientation and whole cation tumbling. The second moments also indicate that the cations are tumbling isotropically at nmr frequencies in the upper half of this temperature range, and suggest that librational oscillation of the whole cation occurs at frequencies at least of the order of 105 s−1 near 150 K. The energy barriers for both methyl group reorientation and isotropic tumbling decrease from chloride to bromide but increase when one goes from bromide to iodide. Powder photograph X-ray diffraction analysis indicates that the chloride and bromide have hexagonal crystal structures (a and c measured), but that the iodide has lower, undetermined symmetry.

NUCLEAR MAGNETIC RESONANCE STUDY OF 205Tl IN MULTIPHASE Tl-Ba-Ca-Cu OXIDE SUPERCONDUCTORS

1988 ◽  
Vol 02 (05) ◽  
pp. 1227-1234 ◽  
Author(s):  
L. Mihály ◽  
K. Tompa ◽  
I. Bakonyi ◽  
P. Bánki ◽  
É. Zsoldos ◽  
...  
Keyword(s):  
Room Temperature ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Nuclear Magnetic Resonance Study ◽  
Spin Lattice Relaxation ◽  
Oxide Superconductors ◽  
X Ray Diffraction ◽  
Magnetic Resonance Study ◽  
X Ray ◽  
Spin Lattice

Several batches of T l- Ba - Ca - Cu oxide superconductors have been synthesized and characterized by resistivity, magnetic susceptibility and X-ray diffraction measurements. The 205 T l NMR line snifts (K), the spin-lattice and spin-spin relaxation times have been measured at room temperature. The temperature dependence of the spin-lattice relaxation rate is also reported. The resonance around K = 0.25 % has a composite line shape indicating the presence of two T l sites. The two sites are tentatively assigned to thallium atoms in the (2223) and (2212) T l- Ba - Ca - Cu phases.

1H NMR Studieson the Molecular Dynamics of Acetylferrocene in Crystals

1988 ◽  
Vol 43 (1) ◽  
pp. 78-80 ◽  
Author(s):  
Atsushi Kubo ◽  
Ryuichi Ikeda ◽  
Daiyu Nakamura
Keyword(s):  
Phase Transition ◽  
Activation Energy ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Lattice Relaxation Time ◽  
Spin Lattice Relaxation ◽  
Scanning Calorimetry ◽  
Two Phase ◽  
Spin Lattice ◽  
Packed Structure

Abstract The temperature dependence of 1H spin-lattice relaxation time was determined at 20 MHz for solid acetylferrocene [(C5H5) (C5H4COCH3)Fe] from ca. 80 K up to the m.p. (359 K). Rather large activation energies of 21 and 24 kJ mol-1 for the C5 reorientations of the two crystallographically nonequivalent non-substituted cyclopentadienyl rings were obtained, indicating that the crystal has a closely packed structure. The two kinds of CH3 groups attached to the substituted cyclopenta­dienyl rings were assumed to be approximately equivalent and gave a low activation energy of 4 kJ mol-1 for the C3 reorientation. No phase transition was observed in the relaxation times or in additional experiments of differential thermal analysis although the presence of two phase transi­tions has been reported previously at temperatures immediately below the melting temperature by means of differential scanning calorimetry.

Phase transitions in solid cycloheptene

1990 ◽  
Vol 68 (4) ◽  
pp. 604-611 ◽  
Author(s):  
Julian Haines ◽  
D. F. R. Gilson
Keyword(s):  
Phase Transition ◽  
High Temperature ◽  
Low Temperature ◽  
Lattice Relaxation ◽  
Proton Spin ◽  
Spin Lattice Relaxation ◽  
Temperature Phase ◽  
Scanning Calorimetry ◽  
Spin Lattice ◽  
Low Temperature Phase

The phase transition behaviour of cycloheptene has been investigated by differential scanning calorimetry, proton spin-lattice relaxation, and vibrational spectroscopy (infrared and Raman). Two solid–solid phase transitions were observed, at 154 and 210 K, with transition enthalpies and entropies of 5.28 and 0.71 kJ mol−1 and 34.3 and 3.4 JK−1, respectively. Cycloheptene melted at 217 K with an entropy of melting of 4.5 JK−1 mol−1. The bands in the vibrational spectra of the two high temperature phases were broad and featureless, characteristic of highly disordered phases. The presence of other conformers, in addition to the chair form, was indicated from bands in the spectra. The ring inversion mode was highly phase dependent and exhibited soft mode type behaviour prior to the transition from the low temperature phase. The low frequency Raman spectra (external modes) of these phases indicated that the molecules are undergoing isotropic reorientation. In the low temperature phase, the vibrational bands were narrow; the splitting of the fundamentals into two components and the presence of nine external modes are consistent with unit cell symmetry of either C2 or Cs with two molecules per primitive unit cell. A glassy state can be produced from the intermediate phase and the vibrational spectra were very similar to those of the high temperature phases, indicating that static disorder was present. The barriers to reorientation, as obtained from proton spin-lattice relaxation measurements, are 9.0 kJ mol−1 in both the high temperature phases, and 15.4 kJ mol−1 in the low temperature, ordered phase. Keywords: cycloheptene, phase transition, differential scanning calorimetry, NMR, vibrational spectroscopy.

Temperature Dependences of NQR Frequencies and Nuclear Quadrupole Relaxation Times of Chlorine in 2,6-Lutidinium Hexachlorotellurate (IV) as Studied by Pulsed NQR Techniques

1990 ◽  
Vol 45 (3-4) ◽  
pp. 485-489
Author(s):  
Keizo Horiuchi ◽  
Takashige Shimizu ◽  
Hitomi Iwafune ◽  
Tetsuo Asaji ◽  
Daiyu Nakamura
Keyword(s):  
Phase Transition ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Spin Lattice Relaxation ◽  
Temperature Phase ◽  
Quadrupole Relaxation ◽  
Spin Lattice ◽  
Resonance Frequencies ◽  
Temperature Dependences ◽  
Nuclear Quadrupole

Abstract The temperature dependences of the 35Cl NQR frequencies vQ and the nuclear quadrupole spin-lattice relaxation times T1Q in 2,6-lutidinium hexachlorotellurate (IV) was observed at various temperatures between 80 and 343 K. This crystal undergoes a phase transition at Tc = 229 K. A single and three pairs of 35Cl NQR frequencies were observed above and below Tc , respectively. The hysteresis of the phase transition and a discontinuity in the temperature dependence of the resonance frequencies at Tc indicate that this phase transition is of first order. Although the resonance frequencies of the pairs in the low temperature phase are very close to one another, T1Q and below Tc could be accurately determined by measuring the Fourier transform spectra of each line. Above ca. 250 K, T1Q showed an exponential decrease which is attributable to the overall reorientational motion of [TeCl6]2- with an activation energy of 82 kJ mol-1

A Nuclear Spin Relaxation Study of the Spin–Rotation Interaction in Symmetric Top Molecules

1972 ◽  
Vol 50 (12) ◽  
pp. 1262-1272 ◽  
Author(s):  
Robin L. Armstrong ◽  
James A. Courtney
Keyword(s):  
Relaxation Times ◽  
Lattice Relaxation ◽  
Relaxation Mechanism ◽  
Spin Rotation ◽  
Spin Lattice Relaxation ◽  
Molecular Reorientation ◽  
Effective Spin ◽  
Spin Lattice ◽  
Simple Exponential Function ◽  
Symmetric Top Molecules

The spin–lattice relaxation times T1 of 1H, 19F, and 31P nuclei were measured in gaseous samples of BF3, CHF3, CH3F, PH3, and NH3 at room temperature for densities from 0.03 to 10 amagat. In several cases the behavior of T1 at the lowest densities snowed deviations from the linear variation characteristic of the extreme narrowing region. The spin–rotation interaction provides the dominant relaxation mechanism in all cases. The data are analyzed on the basis of the assumption that the collision modulated spin–rotation interaction may be described by a single correlation function which is a simple exponential function of time. Values of an effective spin–rotation constant and a cross section for molecular reorientation are obtained for each gas. The results obtained are compared with those available from other types of experiments. This comparison indicates that the theory for spin–lattice relaxation in dilute gases of symmetric top molecules needs to be carefully reassessed.

Chlorine-35 NQR Study of a Structural Phase Transition in (ND4)2PdCl6

1998 ◽  
Vol 53 (6-7) ◽  
pp. 514-517 ◽  
Author(s):  
Yoshio Kume ◽  
Tetsuo Asaji
Keyword(s):  
Phase Transition ◽  
Structural Phase ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Spin Lattice Relaxation ◽  
Temperature Phase ◽  
Spin Lattice ◽  
First Order Phase Transition ◽  
Temperature Dependences ◽  
First Order Phase

Abstract Temperature dependences of 35Cl NQR frequencies and spin-lattice relaxation times were measured at 4.2 to 400 K for natural and deuterated ammonium hexachloropalladate. It was confirmed that only the deuterated salt undergoes a first order phase transition at 30 K. The crystal structure of the low-temperature phase is predicted to be the same as that of the deuterated ammonium hexachloroplatinate and hexachloroplumbate. The mechanism of the deuteration-induced phase transition is discussed.

Structure and Successive Phase Transitions of RGeBr3 (R = Alkylammonium) Studied by Means of NQR

1996 ◽  
Vol 51 (5-6) ◽  
pp. 686-692 ◽  
Author(s):  
Shusaku Gotou ◽  
Tsutomu Okuda ◽  
Toshirou Takahashi ◽  
Hiromitsu Terao ◽  
Koji Yamada
Keyword(s):  
Phase Transitions ◽  
Crystal Structures ◽  
Conduction Mechanism ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Rietveld Analysis ◽  
Spin Lattice Relaxation ◽  
X Ray Diffraction ◽  
Spin Lattice ◽  
Successive Phase

Abstract A series of tribromogermanate(II) complexes RGeBr3 (R = CH3NH3, (CH3)2NH2, (CH3)4N, C2H5NH3, (C2H5)4N) have been synthesized and characterized by 81Br NQR, AC conductivity, DTA, and X-rax diffraction. These measurements revealed the presence of successive phase transitions in these complexes. The crystal structures of Phases I and II in (NH3)4NGeBr3 were derived from the Rietveld analysis of powder X-ray diffraction. The electric conductivity was considerably high in CH3NH3GeBr3 and (NH3)4NGeBr3. The conduction mechanism is discussed on the basis of 81Br NQR spin-lattice relaxation times and crystal structures.

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