Dielectric relaxation and hydrogen bond interaction study of diol-water mixtures

Complex dielectric permittivity measurements in the frequency range 10MHz-20GHz have been carried out in diol-water mixtures over the entire concentration range using a time domain reflectometry (TDR) method at 25°C. A hydrogen bonded theory is applied to compute the dielectric constant for the mixtures. It adequately reproduces the experimental values of static dielectric constants for the diol-water mixtures. The dielectric parameters confirm that the intermolecular homogeneous and heterogeneous hydrogen bonding vary significantly with the increase in concentration of the constituents of the diol-water mixtures.     

Direct measurement of dipole-dipole/CSA cross-correlated relaxation by a constant-time experiment

Relaxation rates in NMR are usually measured by intensity modulation as a function of a relaxation delay during which the relaxation mechanism of interest is effective. Other mechanisms are often suppressed during the relaxation delay by pulse sequences which eliminate their effects, or cancel their effects when two data sets with appropriate combinations of relaxation rate effects are added. Cross-correlated relaxation (CCR) involving dipole-dipole and CSA interactions differ from auto-correlated relaxation (ACR) in that the signs of contributions can be changed by inverting the state of one spin involved in the dipole-dipole interaction. This property has been exploited previously using CPMG sequences to refocus CCR while ACR evolves. Here we report a new pulse scheme that instead eliminates intensity modulation by ACR and thus allows direct measurement of CCR. The sequence uses a constant time relaxation period for which the contribution of ACR does not change. An inversion pulse is applied at various points in the sequence to effect a decay that depends on CCR only. A 2-D experiment is also described in which chemical shift evolution in the indirect dimension can share the same constant period. This improves sensitivity by avoiding the addition of a separate indirect dimension acquisition time. We illustrate the measurement of residue specific CCR rates on the non-myristoylated yeast ARF1 protein and compare the results to those obtained following the conventional method of measuring the decay rates of the slow and fast-relaxing (15)N doublets. The performances of the two methods are also quantitatively evaluated by simulation. The analysis shows that the shared constant-time CCR (SCT-CCR) method significantly improves sensitivity.     

Raman spectroscopy of alkali halide hydration: hydrogen bond relaxation and polarization

The solute–solvent interaction of salts has a striking impact on various biological and industrial processes but its mechanism remains yet mysterious despite intensive studies since 1888 when Franz Hofmeister established the salt series. A combination of confocal Raman spectroscopy and contact angle measurements has enabled us to resolve the hydrogen bond relaxation (O:H―O, HB) and the associated charge polarization dynamics at different molecular site because of alkali halides hydration. Results show consistently that salt hydration softens the O:H phonon but stiffens H―O phonon cooperatively. The extent of HB relaxation and polarization is proportional to the electronegativity difference and ionic radius, following the order of Hofmeister series: X (R/η) = I (2.2/2.5) > Br (1.96/2.8) > Cl (1.81/3.0) > F (1.33/4.0) ≈ 0 for anions, and Y(R/η) = Na (0.98/0.9) > K (1.33/0.8) > Rb (1.49/0.8) > Cs (1.65/0.8) for cations. Observations suggest that ions create each an electric field that aligns, stretches, and polarizes water molecules, which relaxes the O:H―O bond cooperatively, depresses the molecular dynamics, and enhances the hydration shell viscosity and the skin stress. Exercises also demonstrate that Raman spectroscopy performs as a powerful tool for probing the molecular‐site‐resolved HB network relaxation dynamics in terms of phonon stiffness, molecular fluctuation dynamics, and phonon abundance transition under external stimulus. Copyright © 2016 John Wiley & Sons, Ltd.     

Measurement of dipole-dipole cross-correlated relaxation in fast rotating CH2D groups

Studies of protein dynamics are key to understanding their biological function. NMR relaxation studies of proteins to date have focused primarily on characterizing backbone dynamics. In this paper, we focus on the aliphatic side-chains (Ala, Thr, Val, Leu, and Ile) with the goal of deriving dynamical information on the motion of terminal methyl groups. Dipole-dipole cross-correlated cross-relaxation is analyzed in a fast rotating CH(2)D group, as found in partially deuteriated proteins. In comparison with previous studies on AMX spin systems (methylene C(beta)H(2) groups), the fast rotation of the methyl group makes a number of relaxation pathways efficient, through the coherence C(+)H(1)(+)H(2)(-)+C(+)H(1)(-)H (2)(+). Several pulse schemes were designed to evaluate these relaxation rates: the measured values are small and well predicted by taking into account the complete relaxation network, but they remain strongly influenced by 1H-1H relaxation with all protons in the neighborhood of the CH(2)D moiety. The prospects and limitations of this method are discussed in comparison with 2H relaxation measurements.     

Internal dynamics of hydroxymethyl rotation from CH2 cross-correlated dipolar relaxation in methyl-beta-D-glucopyranoside

Conventional relaxation parameters (T1(-1), T2(-1), and NOE), obtained at different temperatures and magnetic fields, are reported for the hydroxymethyl (C6) carbon in methyl-beta-D-glucopyranoside in a D2O/DMSO cryosolvent. These data are interpreted with the Lipari-Szabo model. In addition, two-field measurements of longitudinal and spin-locked relaxation rates related to the cross-correlated carbon-proton dipole-dipole interactions for the same carbon are reported. The complete data set consisting the conventional and cross-correlated relaxation parameters is interpreted using a new "hybrid" approach, in which the Lipari-Szabo model for the auto-correlated spectral densities is combined with the two-site jump model for the cross-correlated spectral densities, with the global correlation time as a common parameter. The two-site jump rates thus obtained are in reasonable agreement with the ultrasonic relaxation measurements, and have reasonable temperature dependence.     

Effects of cross-correlated noises on the relaxation time of the bistable system

The stationary correlation function and the associated relaxation time for a general system driven by cross-correlated white noises are derived, by virtue of a Stratonovich-like ansatz. The effects of correlated noises on the relaxation time of a bistable kinetic model coupled to an additive and a multiplicative white noises are studied. It is proved that for small fluctuations the relaxation time T_c as a function of λ (the correlated intensity between noises) exhibits very different behaviours for αD (α and D, respectively, stand for the ntensities of additive and multiplicative noises). When α>D, T_c increases with increasing λ. But when α相似文献   

Spin-lattice relaxation of nearest neighbor ortho-hydrogen pairs

Specially chosen pulse sequences have been used to isolate the contribution to the nuclear magnetic resonance signal from nearest neighbor oH₂ molecules. Measurements of the rotational diffusion were shown to be consistent with earlier measurements where only oH₂ pairs or only isolated singles could be observed. It was found that the pair magnetization so obtained did not relax exponentially.     

Impurity pairs and excitation relaxation in doped silicon

The kinetics of photoconductivity is studied in silicon doped with B, Al, Ga, In, P, As, and Sb with concentrations of 10₁₆–10₁₈cm_?3 at 4.2 and 10.5 K placed in an 8-mm microwave electric field under pulsed impurity excitation. It is found that infrared absorption by impurity pairs and a slow component of photoresponse relaxation arise at close impurity concentrations. It is shown that this component is due to an increase in the polarization hopping conductivity in the presence of the optical charge exchange of impurity states—isolated impurities and impurity pairs and dipoles (pairs of the major and compensating impurities). The hopping transfer processes of ion charges in the course of relaxation are analyzed. It is shown that the main contribution to polarization photoconductivity comes from hopping transitions in impurity pairs at relatively small concentrations and from hopping with the participation of isolated ions at increased concentrations.     

乙二醇分子间氢键结构与溶剂效应

采用密度泛函理论在B3LYP/6-311++G** (范德华校正)水平上研究乙二醇在气相中分别与乙腈、丙酮、四氢呋喃、水、乙二醇形成氢键二聚体的结构性质,根据PCM 极化统一场模型讨论氢键溶剂效应。结果表明,五种氢键二聚体分子中的氢键属于红移氢键,溶剂使氢键二聚体分子的偶极矩变大,并对OH振动频率的影响不大。     

乙二醇分子间氢键结构与溶剂效应

采用密度泛函理论在B3LYP/6-311++G~(**)水平上研究乙二醇在气相中分别与乙腈、丙酮、四氢呋喃、水、乙二醇形成氢键二聚体的结构性质,根据PCM(polarized continuum model)极化统一场模型讨论氢键溶剂效应.结果表明,五种氢键二聚体分子中的氢键属于红移氢键,溶剂使氢键二聚体分子的偶极矩变大,并对OH振动频率的影响不大.     

Adiabatic and non-adiabatic corrections to properties of the hydrogen molecular cation and its isotopomers: dissociation energies and bond lengths

A study is presented of adiabatic and non-adiabatic corrections to the dissociation energies and bond lengths of H⁺ ₂, D⁺ ₂ and HD⁺ in vibration-rotation levels of their ground electronic states, with particular attention to isotopic scaling. In previous work (MOSS, R. E., 1999, Molec. Phys., 97, 1) on rotationless levels, an anomalous non-adiabatic correction to the bond length was found for v = 20, N = 0 of HD⁺. Other levels close to dissociation are identified that display anomalous non-adiabatic corrections to the dissociation energies and to the bond lengths. The source of these anomalies is discussed.     

Temperature relaxation in hot dense hydrogen

Temperature equilibration of hydrogen is studied for conditions relevant to inertial confinement fusion. New molecular-dynamics simulations and results from quantum many-body theory are compared with Landau-Spitzer predictions for temperatures T with 50相似文献   

Evaluation of the thermodynamic parameters for association process of hydrogen bond complexes from the dielectric relaxation measurements.

A relation between the free energy for dipole relaxation process and that for the association process has been proposed. Using this relation, an equation has been defined for evaluating the association equilibrium constant from the dielectric relaxation measurements. These equations have been applied to study the association of dimethyl sulphoxide and p-tolyl sulphoxide with proton donors (phenol and O-cresol) in an inert solvent carbon-tetra-chloride in the temperature range 298–322K. The calculation of the association equilibrium constant and hence the thermodynamic parameters have shown the wide scope, the proposed relations can be put to in the study of the association process of hydrogen bond complexes.     

C-H,C-N,C-O,N-N的键离解能和键长的计算

用B3LYP/6-311G**和CCSD/cc-pVDZ方法对CH4、CH3、CN、CO、N2、CH3NH2、CH3NO2、NH2NO2八个分子中的C-H、C-N、C-O、N-N键离解能进行计算,通过比较研究可知,计算CH3、CH3NH2、CH3NO2分子中的C-H键离解能和CN、CO、N2分子的键离解能用B3LYP/6-311G**方法可靠,而计算CH3-H、CH3-NH2、CH3-NO2和NH2-NO2分子的键离解能用CCSD/cc-pVDZ方法更可信;用以上二种方法对本文的八个分子的平衡几何结构进行优化求出所需的键长,通过比较可知,CH4、CH3、CN、CO、N2分子用B3LYP/6-311G**的方法进行平衡几何优化求得的键长更可靠,而CH3NO2、NH2NO2、CH3NH2分子则用CCSD/cc-pVDZ方法优化出的键长是更可信.     

Proton tunneling in a hydrogen bond measured by cross-relaxation field-cycling NMR

A field-cycling NMR pulse sequence is described for studying cross-relaxation between unlike nuclear spins in the solid state. The technique has been applied to study proton tunneling in the hydrogen bonds of a carboxylic acid containing 19F and 1H spins. By studying the B-field dependence of the off-diagonal element of the relaxation matrix that characterizes the longitudinal polarizations, an accurate measure of the proton transfer rate is obtained.     

Electromagnetic corrections to the s-wave scattering lengths in pionic hydrogen

Motivated by the recently performed X-ray precision experiments on pionic hydrogen (preceding paper), we reconsider the problem of electromagnetic corrections to the π - N scattering lengths. Based on a relativistic two-channel approach, we find corrections to the π⁻p elastic and single-charge-exchange (SCE) scatering lengths due to the point-Coulomb interaction, the finite-size Coulomb interaction (including the pion size), the first-order vacuum polarization (Uehling potential) and the (π⁻p) - (π⁰n) mass difference (mass difference effect). We also estimate the contribution due to the (γ,n) decay channel. The total corrections to the elastic and the SCE scattering lengths are found to be δ_ε = −(2.1 ± 0.5) × 10⁻² and δ_Γ = −(1.3 ± 0.5) × 10⁻². Previously published values for the corrections are critically compared with our results.