A nuclear magnetic resonance investigation of solid tetraphosphorus trisulphide

The 31 P n. m. r. spectrum and spin–lattice relaxation time in polycrystalline P 4 S 3 have been measured between 77 and 500 K in the range 7 to 25 MHz. In phase II the 31 P n. m. r. spectra and second moments are dominated by the anisotropic chemical shift interactions. Close to the first-order phase transition at 314 K the spectra are narrowed by reorientation of the molecules about their triad axes. This motion also generates anisotropicshift spin-lattice relaxation notable for its absence of frequency dependence. The activation energy of this motion was found to be 34 kJ mol -1 . Nuclear dipolar interactions play only a minor role. In phase 1 the molecules exhibit rapid quasi-isotropic reorientation and diffusion. The anisotropic broadening interactions are averaged out and an AB 3 high-resolution spectrum of a doublet and quartet are resolved at 420 K, well below the melting point, 446 K. In this phase the spin–rotation interaction relaxation mechanism becomes dominant. Taking advantage of the remarkable motional narrowing in this compound we report the first solid-state n. m. r. J spectrum. This spectrum, recorded at 410 K, allowed the J coupling between apical and basal nuclei in solid P 4 S 3 to be measured accurately, 70.4 ± 0.5 Hz.

2002 ◽  
Vol 57 (11) ◽  
pp. 883-887 ◽  
Author(s):  
M. Zdanowska-Fra̡czek ◽  
A. Kozaka ◽  
R. Jakubasb ◽  
J. Wa̡sickia ◽  
R. Utrechta

Temperature-dependent proton NMR relaxation time measurements have been performed at 60 MHz in order to study the NH4+ dynamics in ferroelectric NH4H(ClH2CCOO)2 and mixed Rbx(NH4)1-x(ClH2CCOO)2, where x = 0.15. The data indicate that the dominant relaxation mechanism for the NMR spin-lattice relaxation time T 1 in both crystals involves simultaneous NH4 group reorientation about their C2 and C3 symmetry axis in the paraelectric phase. Details of the NH4+reorientation have been inferred from analysis of temperature dependence of T1 assuming the Watton model. The activation parameters of the motionshave been determined.It has been found that the substitution of Rb does not change the activation parameters of the NH4 group dynamics.


1990 ◽  
Vol 45 (3-4) ◽  
pp. 477-480 ◽  
Author(s):  
Yutaka Tai ◽  
Tetsuo Asaji ◽  
Daiyu Nakamura

Abstract The temperature dependence of the chlorine quadrupole spin-lattice relaxation time T1Q was observed for one of the three 35Cl NQR lines of (pyH)2 MCl6(M = Sn, Pb, Te). Each T1Q curve can be devided into three temperature regions. In the low-and high-temperature regions, T1Q is dominantly determined by the relaxation mechanism due to the libration and reorientation of [MCl6]2- , respectively. In the intermediate temperature region, T1Q results from the modulation of the electric field gradient by the motion of the neighboring pyridinium cations. This way the reorientational motion of the cation between potential wells with nonequivalent depths is precisely characterized.


1969 ◽  
Vol 47 (24) ◽  
pp. 4635-4638 ◽  
Author(s):  
E. Bock ◽  
E. Tomchuk

The spin–lattice relaxation time of the 1,2-dichloroethane molecule has been determined in 6 different nonmagnetic or weakly magnetic solvents at 20 °C, viz: deuterated benzene, carbon disulfide, deuterated 1,2-dichloroethane, carbon tetrachloride, and deuterated chloroform. From the experimental results the relaxation rate in infinitely dilute solution, the so called intramolecular relaxation rate, was determined for each solvent. It was found that the observed intramolecular relaxation rate could be successfully interpreted as arising solely from a dipole–dipole relaxation mechanism. It was further found that the individual differences in the value of the intramolecular spin–lattice relaxation rate of the 1,2-dichloroethane molecule in different solvents could be accounted for in terms of weak complex formation between the solute and solvent molecules.


1979 ◽  
Vol 34 (3) ◽  
pp. 375-379 ◽  
Author(s):  
H. Sterk ◽  
J. Kalcher ◽  
G. Kollenz ◽  
H. Waldenberger

Abstract It is shown that in almost all nitrile carbon-atoms T1 depends first of all on the inter-and/or intramolecular dipol-dipol-relaxation mechanism. Only acetonitrile, as is already known, shows a remarkable dependence on the spin-rotation-relaxation mechanism. This influence is strongly decreasing with an increasing number of atoms, specially hydrogen atoms, in the molecule. The significance of the correlation time r is discussed extensively and the experimental results are verified by calculation of T1 using the viscosity and the inertial moments as parameters.


1966 ◽  
Vol 21 (8) ◽  
pp. 1231-1240 ◽  
Author(s):  
K. Grude ◽  
J. Haupt ◽  
W. Müller-Warmuth

Proton magnetic resonance investigations on solid dimethylether (DM) , diethylether (DE) , dipropylether (DP), diisopropylether (DIP), dibutylether (DB), dimethoxymethane (DMM), diethoxymethane (DEM), dimethoxyethane (DME), diethoxyethane (DEE), acetaldehyde (ACA) and diethylketone (DEK) yielded information on molecular motion, solid state phase transitions and deglassing processes. The temperature-dependence of the spin-lattice relaxation time and the second moment was studied between the melting point and 77 °K using radiofrequency pulse techniques. Both spin-lattice relaxation and line shapes are governed by dipolar interactions which are modulated in time by hindered rotations of CH3-groups. The parameters for this relaxation mechanism are given in detail. Concerning the general results it was possible to distinguish between three cases : a) substances that form only one crystalline phase in the solid state (DM, DIP, DEM, DME, ACA, and DEK); b) ethers that form only a vitreous state (DP and DEE) and c) ethers that form both crystalline and vitreous states depending on the way in which the liquid was cooled. In the last case a pronounced decrease of the second moment of the absorption line was observed near the phase transition from the vitreous to the polycrystalline state. This means that within a small range of temperatures far below the melting point some kind of melting of the glass occurs before the crystal is formed.


1992 ◽  
Vol 47 (1-2) ◽  
pp. 277-282 ◽  
Author(s):  
Keizo Horiuchi ◽  
Daiyu Nakamura

AbstractThe 35Cl NQR spin-lattice relaxation time T1Q, spin-spin-relaxation time T2Q, and 1H NMR spin-lattice relaxation time in the rotating frame T1Q in Mg(H2O) 6SnCl6 were measured as functions of temperature. Above room temperature T2Q increased rapidly with increasing temperature, which can be explained by fluctuations of the local magnetic field at the chlorine nuclei due to cationic motions. From the T1Q experiments, these motions are found to be attributable to uniaxial and overall reorientations of [Mg(H2O)6 ] 2 + ions with activation energies of 95 and 116 kJ mol - 1 , respectively. Above ca. 350 K, T1Q decreased rapidly with increasing temperature, which indicates a reorientational motion of [SnCl6] 2 - ions with an activation energy of 115 kJ mol -1 .


1969 ◽  
Vol 47 (12) ◽  
pp. 2155-2160 ◽  
Author(s):  
P. Wardman ◽  
W. A. Seddon

The spin–lattice relaxation time T1 of electrons (et−) trapped in several ice matrices at 77 °K has been estimated to be of the order of 10−2 s by observation of the electron spin resonance (e.s.r.) dispersion signal under fast passage conditions. These studies, together with measurements of the microwave power saturation of the e.s.r. absorption signal indicate that there is little difference in T1 at 77 °K for et− in solute-free polycrystalline H2O or D2O ice, γ-irradiated 8 M NaOH/H2O or NaOD/D2O glassy ices, and in 8 M NaOD/D2O glasses in which the electrons were produced by photoionization of ferrocyanide ion. This indicates that the predominant spin–lattice relaxation mechanism is not cross relaxation, and that correlations between T1 and line width or trap depth are inappropriate.


1989 ◽  
Vol 44 (4) ◽  
pp. 300-306 ◽  
Author(s):  
Yutaka Tai ◽  
Tetsuo Asaji ◽  
Ryuichi Ikeda ◽  
Daiyu Nakamura

Abstract The 1H NMR second moment M2 and the spin-lattice relaxation time T1 are determined for pyridinium hexachlorotellurate(IV), hexachlorostannate(IV), and hexabromostannate(IV) at various temperatures above ca. 140 K. The phase transition temperatures already reported from halogen NQR experiments are determined as 272, 331, and 285 K, respectively, by differential thermal analysis (DTA). The DTA as well as differential scanning calorimetry measurements show that the above phase transitions are of second-order. For pyridinium hexachlorotellurate(IV) and hexa-bromostannate(I V), a sharp 1H T1 dip was observed at the transition temperature. This is interpreted in terms of a phenomenon related to the critical fluctuation of an order parameter. From the measurements of 1H M2, 60° two-site jumps (60° flips) around the pseudo C6 axis of the cation are suggested to occur in the high temperature phases of the complexes. Modulation of X...1H (X = CI, Br) magnetic dipolar interactions due to the reorientational motion of the complex anions is considered as a possible relaxation mechanism in the high temperature phases.


1975 ◽  
Vol 53 (12) ◽  
pp. 1141-1147 ◽  
Author(s):  
Henry M. van Driel ◽  
Robin L. Armstrong

Calculations of nuclear quadrupolar spin–lattice relaxation times are presented. The expressions obtained for the first order Raman and anharmonic Raman processes are applicable to a pure nuclear quadrupole resonance investigation of the X nuclei in R2MX6 and RMX3 solids. On the basis of realistic assumptions it is shown that the anharmonic Raman process will provide the dominant relaxation mechanism for these nuclei in these compounds. The relation between the spin–lattice relaxation time and the lattice dynamics is obtained explicitly without recourse to an assumed form of lattice vibrational normal mode spectrum. In favorable cases it is shown that the spin–lattice relaxation times can be related to Brillouin zone averaged rotary mode frequencies which are useful for the analysis of experimental data.


1992 ◽  
Vol 47 (1-2) ◽  
pp. 313-318 ◽  
Author(s):  
M. Igarashi ◽  
H. Kitagawa ◽  
S. Takahashi ◽  
R. Yoshizaki ◽  
Y. Abe

AbstractThe spin-lattice relaxation time, T1, of the 23Na-NMR line in NaNO2 is measured between 25 K and 160 K at two magnetic field strengths, 1.1 T and 6.9 T. The temperature dependence of T1 for the center line, observed on a polycrystalline sample prepared by precipitation from aqueous solution, is given by a monotonous curve. T1 increases gradually as the temperature decreases. On the other hand for a single crystal, which is made by a modified Bridgman method, the temperature dependence of T1 shows two deep dips below 150 K and a frequency dependence which cannot be explained by ordinary BPP theory. The dominant relaxation mechanism above and below 150 K is also investigated.


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