Spin-lattice relaxation by tunnelling motions of methyl groups in some organic compounds

The proton spin-lattice relaxation times, T₁, of methyl groups in (CH₃CO)₂O, CH₃COCl, CH₃ COBr and (CH₃)₂S₂ have been measured below melting points at 52 MHz. The observed T₁ minima display the presence of tunnelling rotation. From the fit of the experimental results the ground, the first excited state tunnelling frequencies and the energy difference between the ground and the first excited states of the compounds have been estimated.     

Nuclear spin lattice relaxation in the linear antiferromagnet CsNiCl3

Anisotropic effects have been found in the low temperature (< 10 K) nuclear spin lattice relaxation rates in the linear paramagnet CsNiCl₃ in a strong magnetic field (～ 60 kOe). The existence of a small single ion anisotropy term may be the cause of these effects.     

K-shell excitation of CH4, NH3, H2O,CH3OH,CH3OCH3 and CH3NH2 by 2.5 keV electron impact

The regions around the respective carbon, nitrogen and oxygen K-edges of CH₄, NH₃, H₂O, CH₃OH, CH₃OCH₃ and CH₃NH₂ have been investigated by electron energy loss spectroscopy using a beam of 2.5 keV electrons. All spectra show a number of discrete peaks just below the K-shell ionization threshold. These discrete structures have been interpreted as being associated with the promotion of a K-shell electron to Rydberg orbitals which converge to the K-shell ionization threshold.     

Proton spin lattice relaxation in single crystal of NaH3(SeO3)2

Proton spin lattice relaxation time in NaH₃(SeO₃)₂ was measured at temperatures 300-77 K at a frequency of 8.01 MHz. Except near the temperatures of the ferroelectric transitions at 196 and 100 K the relaxation rate is governed by paramagnetic impurities, and the formula derived by Blumberg for diffusion-limited case is applicable. A logarithmic divergence above 196 K is related to the anomaly of the dielectric constant in the same temperature range.     

Spin-lattice relaxation of CH4 gas in a deuterated clathrate lattice

The proton T₁ temperature dependence of CH₄ gas in a deuterated clathrate lattice deviates from the semiclassifical predictions. The discrepancy is partially accounted for by including the effects of symmetry and the quantization of rotational states.     

Structural characterization,thermal, vibrational properties and molecular motions in perovskite-type diaminopropanetetrachlorocadmate NH3(CH2)3NH3CdCl4 crystal

The work presents a detailed analysis of the sequencing of the structural phase transitions in NH₃(CH₂)₃NH₃CdCl₄ crystal by differential scanning calorimetry (DSC), X-ray, infrared, far infrared and Raman spectroscopy. DSC studies have shown that in analyzed crystal occurring one reversible continuous phase transition at 375/374 K (on heating/cooling). Observed in Nujol and Fluorolube mulls in the wide temperature range between 296 K and 413 K spectral changes through the structural phase transition can be attributed to an onset of motion of cations. An assignment of some bands due to internal modes has been also proposed.     

Intramolecular motions and molecular structure of the CH3 radical

A normal coordinate analysis was carried out for the CH₃ radical to calculate the inertia defects and the centrifugal distortion constants. The calculated values were in fair agreement with the experimental results on the ν₂ band recently obtained by infrared diode laser spectroscopy. Third-order anharmonic potential constants were estimated to calculate vibration-rotation interaction constants and the equilibrium CH bond length. The conventional vibration-rotation interaction theory was extended to assess the effects of the large negative anharmonicity of the ν₂ mode on molecular parameters obtained from the observed spectra. The v₂ dependence of the C rotational constant was discussed by this treatment.     

Crystal structure and thermal behavior of two new organic monosulfates NH3(CH2)5NH3SO4 1.5H2O and NH3(CH2)9NH3SO4 H2O

The chemical preparation, the calorimetric studies and the crystal structure are given for two new organic sulfates NH₃(CH₂)₅NH₃SO₄ 1.5H₂O (DAP-S) and NH₃(CH₂)₉NH₃SO₄·H₂O (DAN-S). DAP-S is monoclinic P2₁/n with unit cell dimensions: a=11.9330(2) Å; b=10.9290(2) Å; c=17.5260(2) Å; β=101.873(1)°; V=2236.77(6) Å³; and Z=8. Its atomic arrangement is described as inorganic layers of units and water molecules separated by organic chains. DAN-S is monoclinic P2₁/c with unit cell parameters: a=5.768(2) Å; b=25.890(10) Å; c=11.177(5) Å; β=115.70(4)°; V=1504.0(11) Å³ and Z=4. Its structure exhibits infinite chains, parallel to the [100] direction where the organic cations are interconnected. In both structures a network of strong and weak hydrogen bonds connects the different components in the building of the crystal.     

Compact Raman CH3F, NH3 optically pumped FIR laser

Conclusion The compact superradiant FIR laser is developed using Herriott cell with long optical path as a FIR cell. The employment of the multipass cell gave an opportunity to increase the IR to FIR conversion efficiency in comparison with traditionally constructed FIR lasers and to observe many intensive FIR lines. The given of multipass cell can be useful for employment in continuously tunable FIR lasers.     

Chloride perovskite layer compounds of [NH3-(CH2)n-NH3]MnCl4 formula

[NH₃-(CH₂)_n-NH₃]MnCl₄ compounds with n = 2, …, 5 are chloride perovskite layer structures. The room temperature phase of members with odd numbers of carbon atoms is orthorhombic, whereas even numbers lead to monoclinic structures. Structural phase transitions were found in all compounds with n > 2. The magnetic behaviour is similar to the (C_nH_2n+1NH₃)₂MnCl₄-family.     

(CH3)2和(NH2)2基团修饰的齐聚苯乙炔分子电子输运性质研究

采用密度泛函理论和非平衡格林函数相结合的方法研究了S原子作为单、双端基的(CH₃)₂-OPE (齐聚苯乙炔)和(NH₂)₂-OPE分子在金电极间的电子输运性质. 通过第一性原理优化计算获得分子部分稳定结构, 再置于Au电极之间构成两极系统, 然后再优化整个两极系统获得稳定结构. 另外, 通过非平衡格林函数方法计算了两极系统的电子输运性质. 计算结果表明, 不同的修饰基团和桥接方式可以导致两极系统的开关效应、负微分电阻行为和整流行为等不同的电子输运性质. 通过计算不同偏压下的分子体系投影轨道电子分布、透射谱、态密度, 对这些新异的电输运性质出现的机理进行了解释.     

On the relaxation rates determining the NH3 and ND3 inversion spectra

A general approach towards the calculation of relaxation rates in the semiclassical approximation is described and applied to a discussion of the NH₃ and ND₃ inversion spectra.     

Pump polarization effect in a superradiant NH3 and CH3F FIR Raman laser

The pump polarization has an evident effect on a superradiant FIR Raman laser both in NH₃ and CH₃F gases when the pump detuning from the resonant line is larger than the Raby frequency. In particular for R resonant lines the circular polarization shows a spontaneous gain about 1.5 times greater than the linear polarization as expected from the theory.     

Magnetic susceptibility studies of (CH2)3(NH3)2FeCl2Br2 and (CH2)6(NH3)2FeCl2Br2

The magnetic susceptibility of the layered compounds (CH₂)₃(NH₃)₂FeCl₂Br₂ and (CH₂)₆(NH₃)₂FeCl₂Br₂ has been measured in the range 80 < T < 300 K. The results follow a Curie-Weiss behavior in the range 120 < T < 300 K but are field dependent for T < 120 K. The results are interpreted in terms of a two-dimensional antiferromagnetic interaction which is canted. A comparison with the corresponding pure chloride compounds is given.     

Impurity-induced magnetic order in the mixture of two spin gap systems (CH3)2CHNH3CuCl3 and (CH3)2CHNH3CuBr3

The ground state of the solid solution of the two spin gap systems (CH₃)₂CHNH₃CuCl₃ and (CH₃)₂CHNH₃CuBr₃ has been investigated by ¹H NMR. The existence of a magnetic ordering in the sample with the Cl-content x=0.85 was clearly demonstrated by a drastic splitting in a resonance line at low temperatures below T_N=13.5 K. The observed NMR spectra in the ordered state was qualitatively consistent with the simple antiferromagnetic state.     

Vibrational relaxation time measurements in CH4 and CH4-rare gas mixtures

With a spectrophone vibrational relaxation times in CH₄ and in mixtures of CH₄ with rare gases were measured. Both the amplitude and the phase method were used. The two infrared active modes of CH₄ (ν₄ and ν₃) were investigated separately. The relaxation times, at one atmosphere, after exciting the lowest mode ν₄, were found to be: τ(CH₄-CH₄) = 1.65 μs; τ(CH₄-He) = 1.97 μs; τ(CH₄-Ne) = 8.6 μs; τ(CH₄-Ar) = 12 μs and τ(CH₄-Kr) ≈ 60 μs. From these values one may in that vibrational-rotational (V-R) energy transfer is the dominant relaxation mechanics. By exciting the higher mode the first step in the deactivation of ν₃ was found to be a V-V transfer to the lowest modes ν₄, ν₂.     

Absolute Raman intensities of CH4, CH3D,CH2D2, CHD3, and CD4

Measurements of the absolute vibrational Raman intensities and depolarization ratios for the fundamental and some overtone and combination bands of CH₄, CH₃D, CH₂D₂, CHD₃, and CD₄ are reported. Experimental aspects of these measurements are discussed. The experimental data conform satisfactorily to all isotope intensity sum rules. The measured intensities and depolarization ratios, together with the vibrational potential function for CH₄, make possible the calculation of the four independent parameters of the isotopic invariant quantities $\text{α}{}^{\mathrm{S}}\text{= |}\text{?α}\text{?S}\text{|}$. The results deduced from these agree with all 36 experimentally observed values. Values of electro-optical parameters for the CH bond are calculated and discussed.     

Line Broadening and Mixing in NH3 Inversion Doublets Perturbed by NH3, He, Ar, and H2

Measurement of absorption by pure ammonia and NH₃–(H₂, He, and Ar) mixtures in the P branch of the ν₄ band at room temperature have been made with a high-resolution Fourier transform spectrometer. Least squares fits of the spectra using different techniques are used for the analysis of the evolution with pressure of the absorption shape for a number of ^PP inversion doublets. Intensities, half-widths, and line-coupling parameters are determined, demonstrating the great importance of line-mixing effects. The results are compared with values calculated using a semiclassical model. The latter explains most of the features of the line-broadening and the J and K dependencies of line-coupling for pure NH₃, whereas poorer results are obtained for line-mixing in mixtures. The most striking and original result is the very large amount of coupling between the symmetric and antisymmetric components, which can reach up to 80% of the width in the case of pure NH₃. Also remarkable is the very strong influence of the rotational quantum number K.     

Nonexponential proton relaxation in (NH4)2 HPO4

Nonexponential relaxation of protons in (NH₄)₂HPO₄ was found from 420 K to 110 K and was interpreted by the three-bath model below 167 K; inter-NH₄ group dipolar coupling above 167 K, and was attributed to non-equivalent NH₄ groups in a molecule.     

Kinetic study of NH3/ND3 exchange in TaS2 by neutron diffraction

Tracer exchange of TaS₂·NH₃ by liquid ND₃ was investigated at 215 and 223 K by neutron diffraction. The results suggest only a molecular exchange on the time-scale of quasielastic neutron scattering measurements.