ESTEM imaging of single atoms under controlled temperature and gas environment conditions in catalyst reaction studies

Heterogeneous gas‐solid catalyst reactions occur on the atomic scale and there is increasing evidence single atoms and very small clusters can act as primary active sites in chemical reactions. Aberration corrected environmental scanning transmission electron microscope (AC ESTEM) has been developed for novel studies of nanoparticle catalysts with Angstrom (0.1 nm) resolution in gas. It extends high vacuum analyses with full analytical facilities and unrestricted high angle annular dark field (HAADF) imaging of single atoms, small clusters and nanoparticles in dynamic in‐situ experiments with controlled gas reaction environments at initial operating temperatures up to > 500 °C.     

Sea level muon spectra at large zenith angles derived from the latest JACEE primary nucleon spectrum

Summary Sea level muon energy spectra at large zenith angles have been derived from the latest JACEE primary spectrum using the Fermilab Single-Arm Spectrometer data on charged-meson production. The role of increasing total cross-section on the final result for the energy spectra has been investigated here with special emphasis. The inclusion of the rising total cross-section at cosmic range of energies, it is seen, has come into much use in explaining the observed data at very high energies. The autors of this paper have agreed not to receive the proofs for correction.     

Violation of the feynman scaling hypothesis and the cosmic-muon charge ratio: a model-dependent analysis

Summary We have attempted here to study the nature of the sea-level cosmicmuon charge ratio at very high energies on the basis of one particular model of multiple production of hadrons in which the violation of the Feynman scaling is one of the very gross features. It is found that extreme emphasis on this feature alone would cause drastic departures from the experimental values of the charge ratio; but when this is combined with some other recently observed and/or proposed characteristics of high-energy interactions the model-based calculations agree quite well up to several TeV energy regime with the data. The model, in the final analysis, supports a very feebly rising nature of the muon charge ratio at ultrahigh energy.     

Lattice imaging of close-packed structures by high resolution electron microscopy: ABO3 perovskite polytypes

Lattice imaging technique of high resolution electron microscopy has been employed to examine 4H, 6H and 9R ABO₃ perovskite polytypes. The lattice images can be correlated with the lattice periodicity and the stacking sequence of AO₃ layers and BO₆ octahedra. The study shows the utility and validity of the lattice imaging technique for the study of relatively close-packed systems. Commonwealth Visiting Professor, University of Oxford (1974–75).     

Biaxial smectic A liquid crystal in a pure compound

The synthesis and characterisation is reported of a low molecular weight organic compound to exhibit the biaxial smectic A (SmAb) phase, which shows a transition from the partial bilayer uniaxial SmAd phase to the SmAdb phase as the temperature is lowered.     

Hetero Diels-Alder reaction: a novel strategy to regioselective synthesis of pyrimido[4,5-d]pyrimidine analogues from Biginelli derivative

A number of potent pyrimido[4,5-d]pyrimidine analogues have been efficiently synthesized by hetero Diels-Alder cycloaddition of 6-methyl-4-phenyl-2-thioxo-1,2,3,4-tetrahydropyrimidine-5-carboxylic acid methyl ester, a Biginelli compound with N-arylidine-N′-methylformamidines and N-arylidine guanidine in dry toluene. Structures of the newly obtained cycloadducts were established on the basis of elemental and spectral (IR, NMR and Mass) data. The molecular mechanism of the observed cycloaddition reaction has been investigated theoretically by means of PM3 semiempirical method. Transition state structure determinations and activation energy calculations have shown the preference for the endo approach over the exo approach of dienophile towards the diene fragments used, which is consistent with the experimental results. The studied cycloadditions proceed via an asynchronous concerted mechanism. It was demonstrated that FMO theory could reasonably predict the relative reactivities between dienes as well as indicating that these reactions belong to normal Diels-Alder type cycloadditions.     

Effective potential model for calculating the energy shift in the ground state of two-electron atoms

An effective operator for the electron–electron interaction derived earlier has been shown to be successful for calculating the ground-state energy shift values for 10 members of the helium isoelectronic sequence in terms of a single free parameter. Some possible applications of the modified interaction operator for semiempirical calculations are suggested.     

Structural,electronic, and magnetic consequences of O-carbonyl vs O-alkoxy ester coordination in new dicopper complexes containing the Cu2(mu-Cl)2 core

The complexes [Cu2(mu-Cl)2(Cl)2(L)2] (L = dialkylpyridine-2,6-dicarboxylate; R = Et, L = depc, 1; R = i-Pr, L = dppc, 2) have been prepared and their magnetic properties studied. The crystal structures of complexes 1 and 2 have been solved. Compound 1 belongs to the P space group with Z = 2, a = 8.3020(10) A, b = 9.2050(10) A, c = 10.065(2) A, alpha = 99.040(10), beta = 100.810(10), and gamma = 106.502(10) whereas 2 belongs to the C2/c space group with Z = 8, a = 11.6360(10) A, b = 25.906(3) A, c = 11.76579(10) A, and beta = 107.900(10). The different alkyl ester substitutes produce substantial structural and electronic differences. The Cu2Cl2 core geometry is planar for 1 whereas it adopts a butterfly shape in the case of 2. Furthermore, in 2 the dppc ligand coordinates only by the carbonyl oxygen atoms whereas in 1 the depc ligand coordinates through carbonyl and alkoxy oxygen atoms. Magnetic susceptibility data show a ferromagnetic coupling between the two Cu(II) centers in both cases (J = 39.9(6) cm(-1) for 1, and J = 51.3(5) cm(-1) for 2) with very weak antiferromagnetic interactions (J ' = -0.59 cm(-1) and -0.57 cm(-1) for 1 and 2, respectively). Theoretical calculations at the extended Hückel level have also been carried out to further understand the electronic nature of complexes 1 and 2.     

Preparation, crystal structure, and thermolysis of phenylenediammonium diperchlorate salts

Three salts of phenylenediammonium diperchlorate have been prepared and characterized by X-ray crystallography. Their thermal decomposition has been studied by thermogravimetry (TG), differential thermal analysis (DTA), and explosion delay (DE) measurements. The kinetics of thermal decomposition was evaluated by model fitting and isoconversional methods using TG data. The oxidation-reduction reactions near the surface of thermolysing perchlorates may be responsible for the decomposition followed by explosion. The possible pathways of thermolysis have also been proposed.     

Carbonation study and determination of cement to sand ratio in hardened cement mortar by X-ray photoelectron spectroscopy

The determination of cement and sand content in an aged cement mortar is a challenging problem for civil engineers. Techniques like x-ray diffraction (XRD), thermogravimetric analysis (TGA) and electrochemical impedance spectroscopy (EIS) are well established, which can give some insight of the hydrated products. The present study is an attempt to use x-ray photoelectron spectroscopy (XPS) technique for the evaluation of ordinary Portland cement (OPC), sand (aggregate) composition and carbonation study in hardened cement mortar. Carbonation analysis and cement to sand ratio for all mortar compositions has been determined and studied in detail in the present work. The C 1s spectra of cement mortar with ratios 1:1, 1:3 and 1:6 shows carbonate formation on the surface with 21, 40 and 32 atomic percent, respectively. An increase in SiO₂ content corresponding to sand is observed for all three mortar mix. The formation of silica gel due to carbonation has not been observed in the mortar samples. The cement to sand ratio for all three mortar mixes is found to be in 20–30 percent error limit due to the heterogeneous nature of the mortar system.