Electron- Spin-Resonance studies of phase transitions in double propionates

Detailed ESR investigations of Mn2+ substituting for Ca2+ in Ca2Sr(C2H5COO)6, (DSP) and Ca2Pb(C2H5COO)6, (DLP) and Ca2Ba(C2H5COO)6, (DBP), in single crystals and powders, over the temperature range from 300°C to -180°C have been carried out to study the successive phase transitions in these compounds. Spectra have been analyzed in terms of axial spin Hamiltonians and the temperature dependences of the parameters studied. Across the I-II transition, new physically and chemically inequivalent sites appear indicating the disappearance of the diad axes on which the propionate groups are located, bringing out the connection between the motional states of the propionate groups and the occurrence of ferroelectricity. The II-III transition also causes chemically inequivalent sites to develop, indicating that the transitions may not be isomorphous as believed previously. Similarities and dissimilarities of the ESR spectra of DLP, DSP and DBP are discussed in relation to the phase transitions.

Study of internal motions through N.Q.R. in 6-Chloropyridin-2-ol

Chlorine-35 n.q.r, has been observed for the first time in 6-chloropyridin-2-ol and its temperature dependence has been studied from 77 K to room temperature. The torsional frequencies and their temperature dependences have been calculated by using Bayer's theory with and without Tatsuzaki's modification.

Electron spin resonance studies of d5 ions (Fe3+ and Mn2+) in lead oxide-lead halide glasses

Electron spin resonance (ESR) of d5 ions (Fe3+ and Mn2+) has been investigated in PbO---PbF2 and PbO---PbCl2 glasses in wide ranges of composition. ESR spectra of d5 ions in these glasses exhibit significant differences which we have attributed to at least three important causes: (i) The ionic potentials of Fe3+ and Mn2+ are different. Hence Fe3+ ions tend to acquire their own environment while Mn2+ ions take up substitutional (Pb2+ ion) positions. (ii) The sizes and nephelauxetic behaviours of O2- and F- ions are similar. Thus even when there is a mixed anionic coordination, the environment of Mn2+ ions is highly symmetrical in oxyfluoride glasses. The Mn2+ spectra in oxychloride glasses are considerably different. (iii) Increase in halide ion concentration increases the ionicity of lead-ligand bonding and favours a more symmetrical environment around dopant ions in halide-rich glasses. The features in ESR spectra have been interpreted in the light of known behaviour of d5 ions in glasses and also in the context of known structural features of PbO---PbX2 glasses. Dopant ions appear to cluster at high concentrations although isolated low-symmetry sites are still observed. Effects of crystallization and annealing upon ESR spectra have also been investigated.

Prediction of frequency and amplitude of foundations at resonance

This note presents the statistical analysis carried out on some of the available experimental results to predict the resonant frequency and maximum displacement amplitude of a machine foundation – soil system under vertical vibration as a function of the size and weight of the foundation and of the excitation level. A total of 442 experimental results of Fry, Novak, and Raman have been analysed using nonlinear regression analysis. The results obtained compared well with predictions obtained from the popular theoretical models, and the coefficient of correlation obtained from the analysis was satisfactory in most of the cases.

Charge-resonance energies in dimer cations of aromatics

t is shown that the charge-resonance contribution to binding of the radical dimer cations of aromatic hydrocarbon decreases as the size of the hydrocarbon molecule increases.

Mechanisms of transmembrane cation transport studied by nuclear magnetic resonance spectroscopy

Several molecules like ionophores, vitamins, ion-binding cyclic peptides, acidic phospholipids, surfactants are known to expose the inner side of vesicles, to the externally added cations. Whereas ionophores and certain other systems bring about these changes by a selective transport (influx) of the cation by specialized mechanisms known as the carrier and channel mechanism, other systems cause lysis and vesicle fusion. These systems have been successfully studied using1H,31 P and13C nuclear magnetic resonance spectroscopy after the demonstration, fifteen years ago, of the ability of paramagnetic lanthanide ions to distinguish the inside of the vesicle from the outside. The results of these ’nuclear magnetic resonance kinetics’ experiments are reviewed.

Forced Oscillations of a Contained Rotating Stratified Fluid

The motion generated by forced oscillations in an incompressible inviscid rotating and/or stratified fluid is examined under linear theory taking the density variation on the inertia terms. The solution consists of numerous internal modes in addition to the mode which oscillates with forcing frequency. Resonance occurs when the forcing frequency is equal to one of the frequencies of the internal modes. Some of these modes grow linearly or exponentially with time rendering the motion unstable and eventually may lead to turbulence. Most of the results discussed here will be missed under Boussinesq approximation.

Pressure dependence of 35Cl nuclear quadrupole resonance in 2,5-, 2,6- and 3,5-dichlorophenols

Pressure dependence of the 35Cl Nuclear Quadrupole Resonances (N.Q.R.) in 2,5-, 2,6- and 3,5-dichlorophenols (DCP) has been studied up to a pressure of about 6·5 kbar at room temperature. While the pressure dependence of the two resonance lines in 2,6-DCP is essentially similar, the lower frequency line in 2,5-DCP is almost pressure independent and the higher frequency line shows a linear variation with pressure upto about 3·5 kbar but shows a negative pressure coefficient beyond this pressure. The two lines in 3,5-DCP have a non-linear pressure dependence with the curvature changing smoothly with pressure. The pressure coefficient for both lines becomes negative beyond a pressure of 5 kbar. The pressure dependence of the N.Q.R. frequencies is discussed in relation to intra- and inter-molecular contacts. Also, a thermodynamic analysis of the data is carried out to determine the constant volume temperature derivative of the N.Q.R. frequency.

Analysis and computation of the oil film thickness between the piston ring and cylinder liner of an internal combustion engine

A study of the essential features of piston rings in the cylinder liner of an internal combustion engine reveals that the lubrication problem posed by it is basically that of a slider bearing. According to steady-flow-hydrodynamics, viz. Image the oil film thickness becomes zero at the dead centre positions as the velocity, U = 0. In practice, however, such a phenomenon cannot be supported by consideration of the wear rates of pistion rings and cylinder liners. This can be explained by including the “squeeze” action term in the

Zeeman effect of nuclear quadrupole resonance in 1-chloro-2,4-dinitrobenzene

The Zeeman effect of NQR was studied in 1-chloro-2,4-dinitrobenzene. A low value of the asymmetry parameter (0.10) was obtained. Four physically inequivalent field gradients were located and their orientations in the crystallographic abc system were determined using symmetry considerations. From these data the orientations of the molecules in the unit cell were determined. The results agree well with the two-dimensional x-ray structural data. The bond characters of the C[Single Bond]Cl bond were calculated, and the values compare well with those generally obtained for C[Single Bond]Cl bonds in chlorine derivatives of benzene. ©1973 The American Institute of Physics.

Zeeman effect of chlorine nuclear quadrupole resonance in mercuric chloride

Abstract is not available.

Conformation of the LL and LD hairpin bends with internal hydrogen bonds in proteins and peptides

The conformation of three linked peptide units having an internal 4 → 1 type of hydrogen bond has been studied in detail, and the low energy conformations are listed. These conformations all lead to the reversal of the chain direction, and may therefore be called as “hairpin bends” or “U-bends”. Since this bend can occur at the end of two chains hydrogen-bonded in the antiparallel β-conformation, it is also known as the “β-bend”. Two types of conformation are possible when the residues at the second and third Cα atoms are both of type L (the LL bend), while only one type is possible for the LD and the DL bend. The LL bend can also accommodate the sequences LG, GL, GG (G = glycine), while the LD bend can accommodate the sequences LG, GD and GG. The conformations for the sequences DD and DL are exact inverses (or mirror images) of those for the sequences LL and LD, respectively, and have dihedral angles (phi2, ψ2), (phi3, ψ3) of the same magnitudes, but of opposite signs as those for the former types, which are listed, along with the characteristics (length, angle and energy) of the hydrogen bonds. A comparison of the theoretical predictions with experimental data (from X-ray diffraction and NMR studies) on proteins and peptides, show reasonably good agreement. However, a systematic trend is observable in the experimental data, slightly deviating from theory, which indicates that some deformations occur in the shapes of the peptide units forming the bend, differing from that of the standard planar peptide unit.