Fluoride‐Bridged {GdIII3MIII2} (M=Cr,Fe, Ga) Molecular Magnetic Refrigerants

The reaction of fac‐[M^IIIF₃(Me₃tacn)]?x H₂O with Gd(NO₃)₃?5H₂O affords a series of fluoride‐bridged, trigonal bipyramidal {Gd^III₃M^III₂} (M=Cr ( 1 ), Fe ( 2 ), Ga ( 3 )) complexes without signs of concomitant GdF₃ formation, thereby demonstrating the applicability even of labile fluoride‐complexes as precursors for 3d–4f systems. Molecular geometry enforces weak exchange interactions, which is rationalized computationally. This, in conjunction with a lightweight ligand sphere, gives rise to large magnetic entropy changes of 38.3 J kg^?1 K^?1 ( 1 ) and 33.1 J kg^?1 K^?1 ( 2 ) for the field change 7 T→0 T. Interestingly, the entropy change, and the magnetocaloric effect, are smaller in 2 than in 1 despite the larger spin ground state of the former secured by intramolecular Fe–Gd ferromagnetic interactions. This observation underlines the necessity of controlling not only the ground state but also close‐lying excited states for successful design of molecular refrigerants.     

Tandem Isomerization and Cationic Copolymerization of Allyl Ethers

Abstract

A new catalyst system comprising a combination of dicobalt octacarbonyl and a hydridosilane has been successfully employed for the tandem isomerization and cationic copolymerization of 1-allyloxy-2-phenoxyethane (M₁) and l-allyloxyoctane (M₂). Reactivity ratios of r₁ = r₂ = 0.58 ± 0.01 were calculated for these monomers by both the Mayo-Lewis and the Fineman-Ross methods which are indicative of a statistical copolymerization. A GPC study of the copolymerization showed that only copolymers were obtained. This data further indicates that the isomerization of the individual monomers and their subsequent copolymerization proceed at very nearly identical rates. The copolymerization of allyl ether monomers presents an opportunity for designing novel polymers with tailored properties.     

On the decay of unparticles

We show that when the unparticle sector is coupled to the Standard Model, unparticle excitations can decay to Standard Model particles. This radically modifies the signals of unparticle production. We present a method for the calculation of the decay lifetimes of unparticles. In a particular model, we show that depending on their lifetime, unparticles can manifest themselves through monojets, delayed events or prompt decays.     

Thermal and optical studies on induced smectic phases of inter molecular hydrogen bonded liquid crystals between decyloxy benzoic acid and citric acid

Hydrogen bonded liquid crystal complex (HBLC) is prepared from mesogenic 4-decyloxy benzoic acid (10OBA) and aliphatic nonmesogenic citric acid (CA). Liquid crystal (LC) phases are investigated by polarizing optical microscopy (POM), differential scanning calorimetry (DSC) studies. Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance spectroscopy (NMR) validate the intermolecular complementary, cyclic type of hydrogen bond (HB) and molecular environment in the designed HBLC complex. Mesomorphic phases like nematic, smectic X (Sm X) and smectic G (Sm G) are characterized by various textures and using different techniques such as POM, DSC and optical tilt angle measurements. Thermal span width and thermal stability factor for the observed phase is calculated. The complexes are prepared in different mole ratio and their corresponding influences on the phase transitions are discussed. Also it is observed that the HB units play a vital role in stabilizing the new Sm X phase. The variation in thermal stability of smectic phases due to the influence of aromatic cores and length of end chain in the different mole ratio of the present HBLC complexes are also discussed. The variation of tilt angle with respect to temperature in the smectic phase has been experimentally calculated and analyzed. The lowered melting and clearing transition temperatures and extended thermal span width in the Sm X phase are also reported.     

Study of vacancy defects and their thermal stability in MeV Fe ion irradiated RAFM steel using positron beam Doppler broadening spectroscopy

Indian reduced activation ferritic-martensitic steel was irradiated with 1.1?MeV Fe ions to various doses from 1 to100?dpa at room temperature. The depth profiling of irradiation-induced vacancy-type defects and the defect-recovery under post-irradiation annealing was studied using variable low-energy positron beam Doppler broadening spectroscopy. The influence of irradiation-induced defects on the microstructural properties was studied by glancing incidence x-ray diffraction (GIXRD) and nanoindentation technique. Positron annihilation study showed the signatures of reduced vacancy concentration at the peak damage region due to injected interstitial effect from 30 to 100?dpa and the widening of vacancy-interstitial recombination-rich region towards the end of ion range with the increase in dose. The GIXRD results were analysed by modified Williamson–Hall plot method, and the variation of coherent domain size and micro-strain with irradiation dose was studied. Irradiation-induced hardening was observed in the nanoindentation study. The features observed in the GIXRD and nanoindentation study are correlated with the depth-resolved defect distribution observed in the positron annihilation study.     

Role of Ab Initio Calculations in the Design and Development of Organometallic Lanthanide‐Based Single‐Molecule Magnets

Single‐molecule magnets based on lanthanides are very attractive due to their potential applications proposed in the area of microelectronic devices. Very recent advances in this area are due to the blend of conventional lanthanide chemistry with organometallic ligands, and several breakthrough achievements are attained with this combination. Ab initio methods based on multi‐reference CASSCF calculations are playing a vital role in the design and development of such molecules. In this minireview, we aim to appraise various contributions in the area of organometallic lanthanide complexes (those containing lanthanide‐carbon bonds) and describe how these robust wavefunction‐based methods have played a constructive role not only in rationalizing the observed magnetic properties but also proven to be a potential predictive tool with some selected examples.     

Some non-perturbative semi-classical methods in quantum field theory (a pedagogical review)

A pedagogical introduction is given to non-perturbative semi-classical methods for finding solutions to quantum field theories. Both the weak coupling method based on a time-independent classical solution, and the WKB method based on all periodic orbits are developed in detail, proceeding ffrom elementary quantum mechanics to field theory in stages. Both methods are then illustrated in model field theories. The [λø⁴]₂ theory to which the weak coupling method is applied yields a new family of “kink” states whose properties are discussed.The WKB method is illustrated by quantizing “soliton” and “doublet” solutions of the two-dimensional sine-Gordon theory. The results are compared to consequences of Coleman's equivalence proof relating this system to the massive Thirring model. The speculation that solitons may be fermions is discussed, along with indications that the WKB method may ne yielding exact mass ratios for this theory.A final section is devoted to solutions of more realistic four-dimensional models containing fermions, internal symmetry etc. Some quark-confinement models and vortex type solutions come under this category. General remarks are made on this family of solutions, and illustrated using 't Hooft's monopole solution.     

Effect of nucleon correlations on pion condensation in neutron stars

It is pointed out that nucleon-nucleon correlations, play an important role in the pion condensation problem. Their effect is estimated by a simple analytical method. It is seen that they inhibit condensation by reducing the attraction a pion might otherwise feel in nuclear matter. Further the effect of correlations increases with nucleon density ?, offsetting the corresponding increase in the attraction felt by pions in free neutron matter.     

An efficient wavelet based spectral method to singular boundary value problems

In this paper, we have established an efficient wavelet based approximation method to nonlinear singular boundary value problems. To the best of our knowledge, until now there is no rigorous shifted second kind Chebyshev wavelet (S2KCWM) solution has been addressed for the nonlinear differential equations in population biology. With the help of shifted second kind Chebyshev wavelets operational matrices, the nonlinear differential equations are converted into a system of algebraic equations. The convergence of the proposed method is established. The power of the manageable method is confirmed. Finally, we have given some numerical examples to demonstrate the validity and applicability of the proposed wavelet method.