Quantitative structure-property relationships in boron nitrides: the 15N- and 11B chemical shifts.

Nuclear Magnetic Resonance (NMR) chemical shifts(delta) for elements in solids may often be approached by ab initio cluster calculations. We employ this technique to investigate the influence of structural alterations on the 15N and 11B chemical shifts in boron nitrides--in both hexagonal and cubic modifications. Within a given class of connectivity, i.e., three- or fourfold coordinated nitrogen, for the first time, an almost linear correlation between the 15N chemical shift and N-B bond lengths could be established. Also, the 11B shifts in hexagonal boron nitride correlate with the B-N bond distance; however, the effect is less pronounced. For the value of the chemical shift (CS), the decisive property is the average bond length at the atom in focus. Variations of CS are predominantly caused by changes in the paramagnetic deshielding. Further, second-nearest neighbor effects on the shieldings at 15N nuclei are quantified by subtraction schemes. The present work is closely related to the verification of models for amorphous high-demand Si/B/N ceramics.     

Solvent polarity and hydrogen-bonding effects on the nitrogen NMR shieldings of N-nitrosamines and DFT calculations of the shieldings of C-, N-, and O-nitroso systems

High-precision nitrogen NMR shieldings, bulk susceptibility corrected, are reported for dimethyl-N-nitrosamine (I) and diethyl-N-nitrosamine (II) in a variety of solvents which represent a wide range of solvent properties from the point of view of polarity as well as hydrogen bond donor and acceptor strength. The observed range of solvent-induced nitrogen shielding variations of (I) and (II) is significant for the amino-type nitrogens, up to about 16 ppm, and originates essentially from the deshielding effect of the increasing polarity of solvent. On the other side, the nitroso nitrogen shieldings reveal an even stronger response to solvent effects, within about 20 ppm, but in this case the increasing polarity and hydrogen bond donor strength of solvent produce enhanced shielding. DFT quantum-mechanical calculations using the GIAO/B3PW91/6-311++G** approach and geometry optimizations employing the same basis set and hybrid density functionals show an excellent correlation with the experimental data on C-, N-, and O-nitroso moieties and reproduce not only major changes but also most of the subtle variations in the experimental nitrogen shieldings of the nitroso systems as a whole. A combination of the calculations involving the corresponding N and O-protonated species and the trends observed in the solvent-induced nitrogen shielding variations shows clearly that the prime acceptor site for hydrogen bonding is the nitroso oxygen atom.     

13C and 1H nuclear spin lattice magnetic relaxation in undoped polyacetylene

Pulsed NMR spin lattice relaxation measurements on ¹³C and ¹H nuclei in undoped trans-polyacetylene have been carried out between 6 and 295 K. The results indicate that the spin lattice relaxation is due to equilibrium fluctuations of the orientational order parameter for the protons while the carbon relaxation can be attributed to their coupling to paramagnetic impurities. In this temperature range no contribution of solitons has been detected in the relaxation mechanisms.     

Ab initio NMR parameters of BrCH3 and ICH3 with relativistic and vibrational corrections

This study is focused on two effects identified when NMR parameters are calculated based on first principles. These effects are 1. vibrational correction of properties when using ab initio optimized equilibrium geometry; 2. relativistic effects and limits of using the Flygare equation. These effects have been investigated and determined for nuclear spin-rotation constants and nuclear magnetic shieldings for the CH₃Br and CH₃I molecules. The most significant result is the difference between chemical shieldings determined based on the ab initio relativistic four-component Dirac-Coulomb Hamiltonian and chemical shieldings calculated using experimental values and the Flygare equation. This difference is approximately 320 ppm and 1290 ppm for ⁷⁹Br and ¹²⁷I in the CH₃X molecule, respectively.     

Model for the evolution of hot and compressed spherical nuclei

A hydrodynamical approach and the Thomas Fermi approximation have been used to study the evolution of hot and compressed nuclei. Spherical symmetry was assumed in the calculation. The dynamical equations have been transformed into “Schrödinger like” equations (using the Madelung transformation) and were solved numerically. Dissipation was simulated in the same way as in the Navier-Stokes equation by introducing shear and bulk viscosities. Global as well as local thermal equilibrium have been studied. The model has been applied to small amplitude oscillations (the breathing mode) and to the stability of hot and compressed nuclei. It was found that compression is more efficient to break nuclei than thermal excitation. The relaxation time for global equilibrium was estimated to be of the order of 10^?22 s. It was found that the results obtained in the case of global and local thermal equilibrium are very similar.     

Nuclear magnetic relaxation and dynamics of biopolymers

A model is proposed in which the NMR relaxation dispersion profiles of biomolecule water solutions are interpreted in terms of magnetic field fluctuations due to the backbone vibrations involving the biopolymer paramagnetic nuclei. This model, which takes into account the experimental evidence which has appeared in the literature for a “fractal-like” density of vibrational state for the protein backbone, has been used to fit some experimental NMR relaxation profiles of biomolecule water solutions. The results obtained are discussed critically in connection with the data reported in the related literature.     

Fluctuations in thermodynamic non equilibrium states

In a statistical theory an expression is derived for the probability of fluctuations in a thermodynamic non equilibrium state. It is a generalization of the Einstein formula, respectively the formula of Greene and Callen for fluctuations in a thermal equilibrium. The application to steady transport processes is discussed in connection with stability conditions.     

A 15N NMR Study of Protonation and Deprotonation of 4,5-Dicyanoimidazole and Its 2-Amino Analogue

Protonation and deprotonation of the title compounds, was studied by means of ¹⁵N NMR. The shieldings of the ring nitrogen atoms are found to be very sensitive to changes in the amount of protonation. In contrast the ¹⁵N shieldings of the cyano and amino groups are found to be relatively insensitive to protonation effects and are unsuitable for estimating the degree of protonation occurring.     

Estimate of the cross section for thermal neutrons

Cross section of the thermal neutrons is considered in the framework of the statistical approach to the complicated nuclei. The probability distribution ?(z = σ/σ*) to have given cross section σ (determined by fluctuations of resonance positions and widths), where σ* is the cross section for the model of equidistant resonances with the same width, has been calculated. The last quantity can be represented in terms of the neutron strength function for given nuclei. The probability distribution ?(z) is universal for all nuclei.     

Anomalous Proton NMR Deshielding in Anilinopyrazoles

In connection with the synthesis of thienobenzodiazepines and certain heterocyclic analogues¹, a number of anilino heterocycle precursors were prepared. Their proton NMR spectra were generally unexceptional with the exclusion of one of the pyrazole isomers which showed a remarkable deshielding of one proton signal in the aniline ring. Further investigations have inferred that this low field shift can be attributed to through speace deshielding by a proximal pyrazole nitrogen lone pair.     

Assessment of Solvent-Induced Nitrogen Shielding Variations of Triazole Systems

High-precision ¹⁴N NMR shieldings are reported for all of the possible N-methyl triazoles in a variety of solvents. A large difference is observed in the effects of solvent on the shieldings of the pyrrole-type and pyridine-type nitrogen atoms in such systems. This difference largely arises from solvent-to-solute hydrogen-bonding effects for the latter type of nitrogen atom. For these two types of nitrogen atoms in triazoles, solvent polarity effects induce changes in the shieldings in opposite directions: this is corroborated by shielding calculations using the solvaton model. Solvent-to-solute hydrogen-bonding effects are larger than those due to solvent polarity and permit the assessment of the basicities of nonequivalent nitrogenous sites; these appear to parallel the analogous basicities with respect to protonation.     

热力学平衡态的涨落判据

任何热力学量的涨落在平衡态下都不能太大.特别地,要求熵和能量的涨落不大,就可以给出低温下热力学平衡态的普遍适用的判据.一些算例表明,低温下即使1023个粒子也不一定能达到热力学平衡态.     

Accurate 13-C and 15-N molecular crystal chemical shielding tensors from fragment-based electronic structure theory

Standard nuclear magnetic resonance (NMR) spectroscopy experiments measure isotropic chemical shifts, but measuring the chemical shielding anisotropy (CSA) tensor can provide additional insights into solid state chemical structures. Interpreting the principal components of these tensors is facilitated by first-principles chemical shielding tensor predictions. Here, the ability to predict molecular crystal CSA tensor components for ¹³C and ¹⁵N nuclei with fragment-based electronic structure techniques is explored. Similar to what has been found previously for isotropic chemical shifts, the benchmarking demonstrates that fragment-based techniques can accurately reproduce CSA tensor components. The use of hybrid density functionals like PBE0 or B3LYP provide higher accuracy than generalized gradient approximation functionals like PBE. Unlike for planewave density functional techniques, hybrid density functionals can be employed routinely with modest computational cost in fragment approaches. Finally, good consistency between the regression parameters used to map either isotropic shieldings or CSA tensor components is demonstrated, providing further evidence for the quality of the models and highlighting that models trained for isotropic shifts can also be applied to CSA tensor components.     

On the theory of fluctuations around non-equilibrium steady states: A generalized time-convolutionless projector formalism

A new method of finding nonlinear Langevin type equations of motion for relevant macrovariables and the corresponding master equation for systems far from thermal equilibrium is presented by generalizing the time-convolutionless formalism proposed previously for equilibrium hamiltoian systems by Tokuyama and Mori. The Langevin type equation consists of a fluctuating force, and the nonlinear drift coefficients which are always identical to those of the master equation. A simple formula which relates the drift coefficients to the time correlation of the fluctuating forces is derived. This is a generalization of the fluctuation-dissipation theorem of the second kind in equilibrium systems and is valid not only for transport phenomena due to internal fluctuations but also for transport phenomena due to externally-driven fluctuations. A new cumulant expansion of the master equation is also obtained. The conditions under which a Langevin and a Fokker-Planck equation of a generalized type for non-equilibrium open systems can be derived are clarified.The theory is illustrated by studying hydrodynamic fluctuations near the Rayleigh-Bénard instability. The effects of two kinds of fluctuations, internal fluctuations of irrelevant macrovariables and external (thermal) noises, on the convective instability are investigated. A stochastic Ginzburg-Landau type equation for the order parameter and the corresponding nonlinear Fokker-Planck equation are derived.     

表面活性剂全氟庚酸和全氟辛酸的19F NMR研究

测定了全氟庚酸(PFHA)和全氟辛酸(PFOA)在三氟三氯乙烷或正戊醇溶液中的不同浓度的¹⁹F NMR 化学位移并归属了谱图. 研究了活性剂浓度对化学位移影响的机理和对不同核的不同影响. 由化学位移δ值对浓度倒数作图,可求得活性剂的临界胶束浓度（cmc）：全氟庚酸：0.0195 mol/L (戊醇溶剂)和0.0406 mol/L（三氟三氯乙烷溶剂）;全氟辛酸：0.0547 mol/L（戊醇溶剂）. 用计算模拟法使δ对浓度倒数作图同实验数据作图相比较,可推测得全氟辛酸戊醇溶液的单体分子与胶束大分子的平衡常数为K=21（mol/L）^-(n-1)和胶束聚集数n=3.9.     

N-芳基取代甲基丙烯酰胺的1H-NMR分析

本文采用酰氯路线由甲基丙烯酰氯同苯胺、对甲苯胺、邻甲苯胺、对溴苯胺、对硝基苯胺、邻硝基苯胺、α-萘胺等反应制得了一系列N-芳基取代甲基丙烯酰胺(N-ArMA).给出了这些新单体的¹H-NMR谱图.研究了这些单体中苯环上不同取代基及同一取代基在不同取代位置上对质子的化学位移的影响.研究结果表明,不同的取代基由于不同的电子效应使苯环上质子峰发生位移,按向低场位移顺序是: -NO₂ >-Br >-H >-CH₃ 同样的取代基在邻位取代使苯环质子移向低场更显著.化学位移的实测值与经验公式计算值比较一致.     

Measurement of thermal diffusivity by magnetic resonance imaging

Nuclear magnetic resonance (NMR) may be used for monitoring temperature changes within samples based on measurements of relaxation times, the diffusion coefficient of liquids, proton resonance frequency or phase shifts. Such methods may be extended to the explicit measurement of the thermal diffusivity of materials by NMR imaging. A method based on measuring nuclear spin phase shifts or changes in the equilibrium nuclear magnetization has been developed for measuring transient thermal diffusion effects and thermal diffusivity with potential applications in NMR thermotherapy and materials science. In this method, a thermal pulse is applied to a medium, and the resultant temporal variations of the nuclear spin phase or of the magnitude of the nuclear magnetization produced by the thermal pulse are monitored at a spatial distance. The results obtained on common fluids agree well with the data from other methods.     

Universal fluctuations in orbital diamagnetism

Bohr–van Leuween theorem has attracted the notice of physicists for more than 100 years. The theorem states about the absence of magnetisation in classical systems in thermal equilibrium. In this paper, we discuss about fluctuations of magnetic moment in classical systems. In recent years, this topic has been investigated intensively and it is not free from controversy. We have considered a system consisting of a single particle moving in a plane. A magnetic field is applied perpendicular to the plane. The system is in contact with a thermal bath. We have considered three cases: (a) particle moving in a homogeneous medium, (b) particle moving in a medium with space-dependent friction and (c) particle moving in a medium with space-dependent temperature. For all the three cases, the average magnetic moment and fluctuations in magnetic moment have been calculated. Average magnetic moment saturates to a finite value in the case of free particle but goes to zero when the particle is confined by a 2D harmonic potential. Fluctuations in magnetic moment shows universal features in the presence of arbitrary friction inhomogeneity. For this case, the system reaches equilibrium asymptotically. In the case of space-dependent temperature profile, the stationary distribution is non-Gibbsian and fluctuations deviate from universal value for the bounded system only.     

Steady state statistics of driven diffusions

We consider overdamped diffusion processes driven out of thermal equilibrium and we analyze their dynamical steady fluctuations. We discuss the thermodynamic interpretation of the joint fluctuations of occupation times and currents; they incorporate respectively the time-symmetric and the time-antisymmetric sector of the fluctuations. We highlight the canonical structure of the joint fluctuations. The novel concept of traffic complements the entropy production for the study of the occupation statistics. We explain how the occupation and current fluctuations get mutually coupled out of equilibrium. Their decoupling close-to-equilibrium explains the validity of entropy production principles.     

Calculation of nuclear magnetic shieldings: infinite-order Foldy–Wouthuysen transformation

A scheme for calculating nuclear magnetic shieldings using the infinite-order Foldy–Wouthuysen (FW) transformation proposed by Barysz and Sadlej (BS) is presented. The nuclear magnetic shieldings of hydrogen halides are calculated by three variant BS schemes; a double finite perturbation method for the external magnetic flux density (B ₀) and the nuclear magnetic dipole moment (? μ _M ) (BS/FPT-2), a single finite perturbation method for B ₀ with analytical differentiation of energy with respect to (? μ _M ) (BS/FPT-1), and an approximate analytical differentiation method with respect to both B ₀ and μ _M (BS/CHF). Although the BS/FPT-2 method is exact theoretically, the actual computation for heavy nuclei includes large error due to reduction of the number of significant figures. The BS/FPT-1 and BS/CHF approaches, on the other hand, yield reasonable values for all of the shieldings. Although several results could not be obtained by the BS/FPT-2 method, no serious contradictions were recognized among these three results. From a comparison of our results with values in the literature, our shieldings for the halogen nuclei are lower than those determined by the four-component relativistic random phase approximation (4-RPA), but the reason for this is not obvious.