| 1 | Author
| Motohiro Mizuno, Tetsuo Asaji, Atsushi Tachikawa, The Late, Daiyu Nakamura | Requires cookie* | | Title
| C  | | | Abstract
| h lo r in e N Q R S p in -L a ttic e R e la x a tio n a n d E le c tro n S p in D y n a m ic s in P a r a m a g n e tic [ C o (H 20) 6] I P tC l 6| Chlorine NQR spin-lattice relaxation times T1Q were determined for [Co(H,0)6][PtCl6] at 4.2 400 K. Above ca. 350 K, T1Q decreased rapidly showing the onset of a reorientation of [PtCl6]2-. The activation energy Ea of this reorientation was determined as 125 ± 15 kJ mol ~1. With decreasing temperature, Tlfi showed a maximum at ca. 250 K. Below ca. 200 K, Tl(. is governed by the magnetic dipolar interaction between chlorines and paramagnetic Co2+ ions and is inversely proportional to the electron spin correlation time re of Co2 . Te is shown to be determined by the electron spin-lattice relaxation time Tle and the temperature independent correlation time rs for the spin-exchange between neighbouring ions above and below ca. 50 K, respectively. The temperature dependence of Tle is explained by assuming the Orbach process with an energy gap A/k of 530 + 20 K as Tle = 5 x 10~14 exp(530/T)s. ts was estimated to be 0.9 x 10"10 s. The temperature dependence of the ESR linewidth of Mn2+ impurities in single crystal was also measured, intending to study Co2+ spin dynamics. The limit of the ESR method is discussed by comparing the obtained results with those of the NQR method. | | |
Reference
| Z. Naturforsch. 46a, 1103 (1991); received September 17 1991 | | |
Published
| 1991 | | |
Keywords
| Spin-lattice relaxation, NQR, ESR, Reorientation, Orbach process | | |
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| default:Reihe_A/46/ZNA-1991-46a-1103.pdf | | | Identifier
| ZNA-1991-46a-1103 | | | Volume
| 46 | |
2 | Author
| Silvia Wigand, Tetsuo Asaji, Ryuichi Ikeda, Daiyu Nakamura | Requires cookie* | | Title
| Reorientational Motion of Trihalogenomethyl Groups in Organic Compounds as Studied by 35 C1 NQR and 19 F NMR Spectroscopy  | | | Abstract
| Trihalogenomethyl derivatives of 4-chloroacetanilide, 4-ClC6HfNHCOCCl3,4-ClC6H4NHCOCF2Cl, and 4-ClC6H4NHCOCF3 were prepared. The 35 C1 NQR and 79 F NMR spin-lattice relaxation times T1Q and T1F, respectively, of these compounds were measured at various temperatures. On heating, T1Q of the CC13 and CF2C1 groups decreased rapidly above ca. 110 and 150 K, respectively, showing the onset of reorientation of the trihalogenomethyl group about the pseudo-triad axis. The activa-tion energies were determined to be 27 and 13kJmol _1 for the CC13 and CF2C1 reorientation, respectively. The temperature dependences of the 19 F NMR T1F of the CF2C1 and CF3 groups lead to activation energies of 13 and 4.3 kJ mol~ 1 , respectively, for the same reorientations. T1F of the CF3 group observed above ca. 200 K was attributed to the spin-rotational interaction. The TIQ 1 of ring-chlorine in 4-ClC6H4NHCOCCl3 and 4-ClC6H4NHCOCF3 can be interpreted by the T" law with « = 2.2 and 1.1, respectively, whereas that of 4-ClC6H4NHCOCF2Cl by the sum of two contributions: T" law (n = 2.0) and the modulation mechanism due to the CF2C1 reorientation. | | |
Reference
| Z. Naturforsch. 47a, 265—273 (1992); received July 19 1991 | | |
Published
| 1992 | | |
Keywords
| Spin-lattice relaxation, NQR, NMR, Reorientational motion | | |
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| default:Reihe_A/47/ZNA-1992-47a-0265.pdf | | | Identifier
| ZNA-1992-47a-0265 | | | Volume
| 47 | |
4 | Author
| Tetsuo Asaji, Keizo Horiuchi, Takehiko Chiba, Takashige Shimizu, Ryuichi Ikeda | Requires cookie* | | Title
| NMR * NQR and DTA * DSC Studies of Phase Transitions in Pyridinium Tetrachloropalladate(II) and Pyridinium Tetrachloroplatinate(II)  | | | Abstract
| From the measurements of DTA • DSC and the temperature dependences of 35 C1 NQR frequen-cies, phase transitions were detected at 150 K, 168 K, and 172 K for (pyH) 2 [PtCl 4 ], and at 241 K for (P yH) 2 [PdCl 4 ], In order to elucidate the motional state of the constituent ions in the crystals in connec-tion with the structural phase transitions, the 35 C1 NQR and 'H NMR spin-lattice relaxation times and the second moment of the 'H NMR line were measured as functions of temperature. For both com-pounds, the potential wells for the cationic reorientation are suggested to be highly nonequivalent at low temperatures. Above 168 K, the pyridinium ions in (pyH) 2 [PtCl 4 ] are expected to reorient between almost equivalent potential wells. As for (pyH) 2 [PdCl 4 j, it is expected that the orientational order of the cation still remains even above the second order transition at 241 K. A change of the potential curve from two-unequal to three-unequal wells is proposed as a possible mechanism of the second order tran-sition. The activation energies for the cationic motion in the respective model potential are derived for both compounds at high and low temperatures. | | |
Reference
| Z. Naturforsch. 53a, 419—426 (1998); received December 30 1997 | | |
Published
| 1998 | | |
Keywords
| Phase transition, NQR, NMR, Spin-lattice relaxation, DSC | | |
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| default:Reihe_A/53/ZNA-1998-53a-0419.pdf | | | Identifier
| ZNA-1998-53a-0419 | | | Volume
| 53 | |
5 | Author
| H. Nishihara, T. Kanomata, K. Sato, N. Suzuki, T. Harada | Requires cookie* | | Title
| NMR of 51 V in VRuP: Possible Onset of Charge-Density-Waves  | | | Abstract
| NMR experiments are reported for VRuP which has an orthorhombic TiNiSi structure and shows anomalies in the temperature dependence of the electric conductivity and static susceptibility. A field-swept spectrum of 5 'V perturbed by a quadrupole interaction has been observed, which shows no anomalous temperature dependence. However, the metallic spin-lattice relaxation rate decreases in a stepwise fashion with decreasing temperature at around 200 K, in accordance with the resistivity and the susceptibility data, suggesting a possible CDW formation in this material. | | |
Reference
| Z. Naturforsch. 53a, 524—527 (1998); received January 26 1998 | | |
Published
| 1998 | | |
Keywords
| NMR, CDW, VRuP, 51 V, Spin-Lattice Relaxation | | |
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| default:Reihe_A/53/ZNA-1998-53a-0524.pdf | | | Identifier
| ZNA-1998-53a-0524 | | | Volume
| 53 | |
6 | Author
| Makoto Kaga, Piotr Koziol, Tetsuo Asaji, Daiyu Nakamura | Requires cookie* | | Title
| Electric field Gradient Modulation by Motion of Lone-Pair Electrons in [(CH 3 ) 3 S] 2 MC1 6 (M = Pt, Sn) as a Possible Relaxation Mechanism of Chlorine Nuclear Quadrupole Resonance  | | | Abstract
| The temperature dependence of the chlorine NQR spin-lattice relaxation time T^was observed for trimethylsulfonium hexachlorometallates(IV), [(CH 3) 3 S] 2 MC1 6 (M = Pt, Sn), trimethylammonium hexachlorostannate(IV), [(CH 3) 3 NH] 2 SnCl 6 , and tetramethylphosphonium hexachlorostannate(IV), [(CH 3) 4 P] 2 SnCl 6 . The quadrupolar relaxation in [(CH 3) 3 NH] 2 SnCl 6 and [(CH 3) 4 P] 2 SnCl 6 can be described by the usual librational and reorientational motion of the complex anion at lower and higher temperatures, respectively. Besides T 1Q due to these two mechanisms, T 1Q minimum was observed at ca. 90 and 120 K for [(CH 3) 3 S] 2 PtCl 6 and [(CH 3) 3 S] 2 SnCl 6 , respectively, which is attributable to the electric field gradient modulation by the motion of the [(CH 3) 3 S] + cation having lone-pair electrons. The activation energies for the isotropic reorientation of the complex anion were determined as46,65, 59, and 60 kJ mol^ for [(CH 3) 4 P] 2 SnCl 6 , [(CH 3) 3 NH] 2 SnCl 6 , [(CH 3) 3 S] 2 PtCl 6 , and [(CH 3) 3 S] 2 SnCl 6 , respectively. | | |
Reference
| Z. Naturforsch. 45a, 1033—1037 (1990); received May 26 1990 | | |
Published
| 1990 | | |
Keywords
| Nuclear Quadrupole Resonance, Spin-Lattice Relaxation, EFG Modulation, Lone-Pair Electrons | | |
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| default:Reihe_A/45/ZNA-1990-45a-1033.pdf | | | Identifier
| ZNA-1990-45a-1033 | | | Volume
| 45 | |
7 | Author
| D. Brinkmann | Requires cookie* | | Title
| Probing the Electronic Structure of Y-Ba-Cu-O Superconductors by Copper NQR/NMR  | | | Abstract
| The paper discusses some NQR/NMR studies performed on Y-Ba-Cu-O superconductors at the University of Zürich. It is shown how the resonance methods can yield information on electronic properties of quite different character. The review deals with: (1) the temperature and pressure dependence of Cu NQR frequencies in YBa 2 Cu 4 O g (1-2-4); (2) an NQR study of the properties of Ca substituted 1-2-4; (3) the temperature dependence of the Cu Knight shifts in 1-2-4; (4) the NMR of plane Cu2 in the paramagnetic state of YBa 2 Cu 3 0 6 ; (5) the dependence on temperature, pressure and orientation of the Cu spin-lattice relaxation in 1-2-4. | | |
Reference
| Z. Naturforsch. 47a, 1—6 (1992); received September 20 1991 | | |
Published
| 1992 | | |
Keywords
| NQR, NMR, High-temperature superconductors, Knight shift, Spin-lattice relaxation | | |
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| default:Reihe_A/47/ZNA-1992-47a-0001.pdf | | | Identifier
| ZNA-1992-47a-0001 | | | Volume
| 47 | |
8 | Author
| Makoto Kaga, Tetsuo Asaji, Ryuichi Ikeda, Daiyu Nakamura | Requires cookie* | | Title
| Chlorine Nuclear Quadrupole Relaxation and Cationic Motion in Trimethylsulfonium Hexachloroselenate(IV): [(CH 3 ) 3 Sl 2 SeCl^  | | | Abstract
| The 35 C1 NQR spin-lattice and spin-spin relaxation times, 7^ and T2Q, respectively, and the 'H NMR spin-lattice relaxation time T1H at 32 and 60 MHz were determined for [(CH3j3S]2SeCl6 as functions of temperature. The rapid decrease of observed above ca. 250 K with increasing temperature was attributed to the onset of reorientation of the [SeCl6] 2 " complex anion with the activation energy £a = 42 + 5 kJ mol -1 . When cooled from ca. 250 K, T1Q showed an anomalous decrease. This 7"1Q decrease was explained by electric field gradient modulation related to some cationic motion. Possible origins of the cationic motion are discussed. | | |
Reference
| Z. Naturforsch. 47a, 274—276 (1992); received July 19 1991 | | |
Published
| 1992 | | |
Keywords
| Spin-lattice relaxation, NQR, NMR, EFG modulation, Molecular motion | | |
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| default:Reihe_A/47/ZNA-1992-47a-0274.pdf | | | Identifier
| ZNA-1992-47a-0274 | | | Volume
| 47 | |
9 | Author
| Takashige Shimizu, Tetsuo Asaji, Daiyu Nakamura, Ryuichi Ikeda | Requires cookie* | | Title
| Uniaxial Reorientation of Octahedral Complex Anions Excited in Triethylammonium Hexachlorostannate (IV) Crystals  | | | Abstract
| The temperature dependence of the 35 C1 NQR spin-latticew relaxation time T1Q has been deter-mined for the three resonance lines observed in [(C2H5)3NH]2SnCl6. The higher frequency lines fade out around 150 K upon heating, whereas the lowest line shows up to room temperature no anomaly, although these three lines are assigned to chlorines belonging to the same complex anion. The T1Q values of the higher two lines decrease exponentially around the fade-out temperature, where T iq of the lowest line shows no such behavior. These results are explained by the onset of uniaxial reorientations of the octahedral complex ions by 90° about the Cl-Sn-Cl axis containing the lowest frequency chlorines. The activation energy (£J of this reorientation (22-24 kJ moP 1) is the lowest so far reportd for [SnCl6] 2-ions. £a about the other axes is 67 kJ mop 1 , indicating a remarkable anisotropic reorientation. | | |
Reference
| Z. Naturforsch. 47a, 283—287 (1992); received July 19 1991 | | |
Published
| 1992 | | |
Keywords
| Spin-Lattice Relaxation, NQR, NMR, Reorientational Motion, Hydrogen Bond | | |
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| default:Reihe_A/47/ZNA-1992-47a-0283.pdf | | | Identifier
| ZNA-1992-47a-0283 | | | Volume
| 47 | |
10 | Author
| Takeshi Kyan, Hamagawa, Takahiro Isono, Masao Hashimoto | Requires cookie* | | Title
| Hiroshi  | | | Abstract
| The crystal structure of cyclohexylhemiacetal (cycHx-CH) was determined at 296 K: monoclinic, space group P2 Jc, a =1028.7 (9), b = 609.5 (1), c = 1811.9 (4) pm, and ß = 99.79 (3)°, Z -4, R = 0.0552. The three 5s Cl NQR lines in cycHx-CH, T., T2, and T2*, were measured by a pulsed method at 80-300 K. Below 200 K Tf 1 obeyed the T law well, indicating that the spin lattice relaxation is governed by lattice vibrations. The reorientation of CC13 seems to be responsible for the sharp T: drop observed above 250 K. Shoulders in the T { vs. 1/T curves indicate the presence of Ti minima at about 240 K. A fluctuation of the EFG due to a dynamic disorder of hydrogen atoms in the OH groups is assumed to explain the T x minima. | | |
Reference
| Z. Naturforsch. 47a, 299 (1992); received July 25 1991 | | |
Published
| 1992 | | |
Keywords
| Chlorine NQR, Spin-lattice relaxation, Hydrogen bond, Crystal structure | | |
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| default:Reihe_A/47/ZNA-1992-47a-0299.pdf | | | Identifier
| ZNA-1992-47a-0299 | | | Volume
| 47 | |
11 | Author
| Haruo Niki, Hirotaka Odahara, Katsuji Tamaki, Masao Hashimoto | Requires cookie* | | Title
| Inequivalent Reorientation of the Trichloromethyl Groups in l,4-Bis(TrichloromethyI) Benzene as Studied by Pulsed 35C1NQR  | | | Abstract
| The temperature dependence of Ti of 35C1 N Q R o f the title com pound evidenced that the three crystallographically inequivalent CC13 groups have different potential barriers against reorientation (about 30, 36, and 42 kJ/mol). An intramolecular interaction between rc-electrons on the benzene ring and the C -C l bond is proposed to interpret the characteristic frequency splitting com m on to the 35C1 N Q R spectrum of each of the three inequivalent CC1? groups. The magnitude of T2 of each Cl atom is interpreted by intra-and intermolecular H • • • Cl interactions. It was found that only part of the temperature dependence of the N Q R frequency can be interpreted by reorientation. | | |
Reference
| Z. Naturforsch. 49a, 273—2 (1994); received July 23 1993 | | |
Published
| 1994 | | |
Keywords
| Chlorine NQ R, Spin lattice relaxation, Transeverse relaxation, M olecular structure | | |
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| default:Reihe_A/49/ZNA-1994-49a-0273.pdf | | | Identifier
| ZNA-1994-49a-0273 | | | Volume
| 49 | |
12 | Author
| Masao Hashimoto, Shuji Matsumoto, Masakazu Kunitomo, Haruo Niki, Hirotaka Odahara, Katsuji Tamaki | Requires cookie* | | Title
| 35C1 NQR Relaxation and Hydrogen Bond in Some Chloral Hemiacetals  | | | Abstract
| The crystal structure of chloral ethylhemiacetal has been determined at 291 K: monoclinic, space group C f -P 2 lt Z = 2, a = 854.5(1), b = 594.0(3), c = 853.3(1) pm, ß = 108.30(2)°, R = 0.0962. A sharp decrease of the spin lattice relaxation time 7i found for the 35C1 N Q R o f the CC13 groups in chloral methyl-, ethyl-and n-heptylhemiacetals is attributed to the onset of reorientation of the group over a potential barrier o f ca. 39, 37, and 32 kJ/m ol, respectively. An unusual vs. 1/T curve with a 7i minimum superimposed on the sharp decrease of 7\ due to the reorientation was observed for each of the three Cl N Q R lines of nH p-C H . This phenom enon is tentatively ascribed to a fluctuation of EFG caused by jum ping m otion o f the hydrogen atom s in the OH groups. | | |
Reference
| Z. Naturforsch. 49a, 279 (1994); received August 16 1993 | | |
Published
| 1994 | | |
Keywords
| Crystal structure, Hydrogen bond, Chlorine N Q R, Spin lattice relaxation | | |
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| default:Reihe_A/49/ZNA-1994-49a-0279.pdf | | | Identifier
| ZNA-1994-49a-0279 | | | Volume
| 49 | |
13 | Author
| Masao Hashimoto, Takahiro Isono, Noriko Yomesaka, Haruo Niki, Hiroshi Kyan, Takeshi Hamagawa | Requires cookie* | | Title
| Reorientation of the CC1 3 Group in Chloral 4-Chlorobenzyl- hemiacetal. A Pulsed 35 C1 NQR and X-ray Study  | | | Abstract
| The crystal structure of the title compound was determined at 291 K: monoclinic, space group C^h-P21/n, Z = 4, a = 1693.2(1), 6 = 579.3(1), c = 1232.5(1) pm, and ß = 107.21 (1)°, R = 0.0415. A sharp decrease of of Cl NQR found at T> 270 K for the CC13 group is attributed to the reorientation of the group over a potential barrier of ca. 50 kJ/mol. Intermolecular interactions between the CC13 and the neighboring atoms seem to dominate the magnitude of the potential barrier. T{~ 1 of the 35 C1 NQR of the Cl atom on the benzene ring obeyed the T 2 law well in the range 80 < T/K <270, while at T>280 K it deviated from the T 2 law. | | |
Reference
| Z. Naturforsch. 47a, 293—298 (1992); received July 25 1991 | | |
Published
| 1992 | | |
Keywords
| Crystal structure, Hydrogen bond, Chlorine NQR, Spin lattice relaxation, Atom-atom potential method | | |
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| default:Reihe_A/47/ZNA-1992-47a-0293.pdf | | | Identifier
| ZNA-1992-47a-0293 | | | Volume
| 47 | |
15 | Author
| Stefan Jurga, Kazimierz Jurga, EduardC. Reynhardt, Piotr Katowski | Requires cookie* | | Title
| A Proton NMR Study of n-Decylammonium Chain Dynamics in the Perovskite-type Layered Compound (C 10 H 21 NH3) 2 CdCl4  | | | Abstract
| A detailed proton second moment and spin-lattice relaxation time investigation of the bilayered compound (C 10 H 21 NH 3) 2 CdCl 4 is reported. In the low temperature phase the methyl group exe-cutes a classical threefold reorientation, while the NH 3 group is involved in a similar reorientation in an asymmetric potential well. Evidence for defect chain motions in this phase has been found, and infomation regarding the potential wells associated with these motions has been extracted from the data. In the high temperature phase, slow chain defect motions and fast fourfold reorientations of chains about their long axes, parallel to the normal to the bilayer, have been observed. | | |
Reference
| Z. Naturforsch. 48a, 563—569 (1993); received October 9 1992 | | |
Published
| 1993 | | |
Keywords
| Bilayered compounds, Phase transition, Spin-lattice relaxation, Molecular motions, Defect motions | | |
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| default:Reihe_A/48/ZNA-1993-48a-0563.pdf | | | Identifier
| ZNA-1993-48a-0563 | | | Volume
| 48 | |
16 | Author
| Tetsuo Asaji, Hideshi Tomizawa, Ryuichi Ikeda | Requires cookie* | | Title
| Structural Phase Transition of N,N-Dimethylnitramine as Studied by 14N Nuclear Quadrupole Resonance  | | | Abstract
| The 14N nuclear quadrupole relaxation time and resonance frequencies v+, v_, and vd of N,N-dimethylnitramine were measured between 14 and 313 K. The frequency increase of v+ and v_ observed below Tc (108 K) is explained by the increase o f prc electrons in the am ino nitrogen caused by the deformation of the m olecular skelton, which is planar above Tc. The sharp Tip minima for v+ and v_ observed at Tc are attributed to the softening o f vibration modes on both sides of Tc. The fluctuation o f the nitrogen-hydrogen m agnetic dipolar interaction due to C H 3 reorientation was detected as a broad T'lQ minimum observed around 84 K. A logarithmic divergence of Tu31 observed on the high-temperature side o f Tc suggests the presence o f a diffusive or overdamped-type soft mode. | | |
Reference
| Z. Naturforsch. 49a, 253 (1994); received August 10 1993 | | |
Published
| 1994 | | |
Keywords
| M olecular crystal, Phase transition, Soft mode, NQ R, Spin-lattice relaxation | | |
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| default:Reihe_A/49/ZNA-1994-49a-0253.pdf | | | Identifier
| ZNA-1994-49a-0253 | | | Volume
| 49 | |
17 | Author
| Hisashi Honda, Shin'. Ichi Ishimaru, Noriko Onoda-Yamamuro, Ryuichi Ikeda | Requires cookie* | | Title
| D  | | | Abstract
| y n a m ic s o f N i t r i te I o n s in th e I o n ic P la s tic C r y s ta l T IN O 2 s tu d ie d b y 15N a n d 205T1 N The temperature dependences of the NMR spin-lattice and spin-spin relaxation times and the NMR spectra of 15N in T115N02 were observed in the plastic phase (282.4 K < T < 459 K) and the low-temperature phase. From the analysis of 15N NMR data, we attributed the motion reported in dielectric and TI NMR studies in the low-temperature phase to the 180°-flip of NO^~ ions which takes place with an activation energy of 14 kJ mol-1. In the plastic phase, we detected isotropic NOJ reorientation with an activation energy of 13.5 kJ mol-1 and a new anionic motion with 10 kJ mol-1. | | |
Reference
| Z. Naturforsch. 50a, 871—875 (1995); received June 16 1995 | | |
Published
| 1995 | | |
Keywords
| Solid NMR, Spin-lattice relaxation, Plastic crystal, Phase transition, Chemical shift anisotropy | | |
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| default:Reihe_A/50/ZNA-1995-50a-0871.pdf | | | Identifier
| ZNA-1995-50a-0871 | | | Volume
| 50 | |
20 | Author
| Hiroshi Miyoshi, Keizo Horiuchi, Narumi Sakagami, Kenichi Okamoto, Ryuichi Ikeda | Requires cookie* | | Title
| C1 NQR, *H NMR, and X-Ray Diffraction Studies in a Hydrogen Bonded Complex Na 2 PtCl 6 * 6H z O  | | | Abstract
| The 35 C1 NQR frequencies, spin-lattice relaxation time and X H NMR relaxation time were measured on crystalline Na 2 PtCl 6 • 6H z O at 77-350 K. The presence of three nonequivalent chlo-rine sites found by X-ray diffraction measurement is in agreement with the observed three NQR lines, which have different temperature dependences attributable to differences in the direction of H-bonding with water molecules. The three NQR lines correspond to three kinds of chlorines with different Pt-Cl distances and H-bond directions. | | |
Reference
| Z. Naturforsch. 53a, 603—607 (1998); received October 31 1997 | | |
Published
| 1998 | | |
Keywords
| CI NQR, X-Ray Diffraction, Spin-Lattice Relaxation, Quadrupole Coupling Constant, Hydrogen Bond | | |
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| default:Reihe_A/53/ZNA-1998-53a-0603.pdf | | | Identifier
| ZNA-1998-53a-0603 | | | Volume
| 53 | |
|