DISTORTIONS INDUCED BY A MAGNETIC FIELD IN PLANAR ALIGNED SAMPLES OF SMECTIC-C LIQUID CRYSTALS

Abstract

This article presents some preliminary theoretical results for the onset of the Helfrich-Hurault transition in smectic-C liquid crystals induced by a magnetic field applied parallel to the smectic layers. An energy in terms of the smectic layer displacement u is minimized via averaging to enable the calculation of a critical field strength H _c for the onset of layer distortions.     

STRUCTURAL STUDIES ON PYRAZOLYLPYRIDINE LIGANDS AND COMPLEXES. 2. COMPARISONS BETWEEN BISPYRAZOLYLPYRIDINE LINKAGE ISOMERS AND WITH 2,2′,6′,2″-TERPYRIDINE JERZY ZADYKOWICZ

Abstract

Crystal structures were obtained for the 3(C),2′;6′,3″(C)-linked bispyrazolylpyridines 2,6-di(2H-4,5,6,7-tetrahydroindazol-3-yl)pyridine (1), 2,6-di(l-methyl-4,5,6,7-tetrahydroindazol-3-yl)pyridine (2), 2,6-di(1 -(4-ethoxycarbonylphenyl)-4,5,6,7-tetrahydroindazol-3-yl)pyridine (3) and for the homoleptic Ru^II complex of 2, [Ru(2)₂]Cl₂, which crystallized with 7 molecules of CHCl₃. Ligand 1 adopts the inter-and intramolecularly hydrogen-bonded syn,syn rotameric conformation, while 2 and 3 were in the anti,anti forms. Relative to the latter, iigand distortions were assessed in 1 (considered as a H⁺ complex) and [Ru(2)₂]Cl₂. Comparisons were drawn with other tridentate ligands containing a pyridine nucleus, specifically the 1(N),2′;6′,1″(N″) linkage isomers and 2,2′;6′,2″-terpyridine, in both free and Ru^II complexed forms, as well as with their bidentate analogues. Unlike with bidentate ligands, the bonds to the pyridine moiety are shortest, the outer heterocyclic rings are drawn inward and, overall, the ligands remain fairly planar. Flanking substituents remain well splayed out in the 1,2′;6′,1″-linked bispyrazolylpyridines, are more parallel in the 3,2′;6′,3″ linkage isomers and are unfavorably compressed in terpyridines.     

Analysis of pseudo jahn–teller distortion based on natural bond orbital theory: Case study for silicene

Ground state (GS) instability of nondegenerate molecules in high symmetric structures is understood through Pseudo Jahn–Teller mixing of the electronic states through the vibronic coupling. The general approach involves setting up of a Pseudo Jahn–Teller (PJT) problem wherein one or more symmetry allowed excited states couple to the GS to create vibrational instability along a normal mode. This faces two major complications namely (1) estimating the adiabatic potential energy surfaces for the excited states which are often difficult to describe in case the excited states have charge-transfer or multi-excitonic (ME) character and (2) finding out how many such excited states (all satisfying the symmetry requirements for vibronic coupling) of increasing energies need to be coupled with the GS for a particular PJT problem. An analogous alternative approach presented here for the well-known case of symmetry breaking of planar (D_6h) hexasilabenzene (Si₆H₆) to the buckled (D_3d) structure involves identifying the second-order donor–acceptor, hyperconjugative interactions (E²_{i → j}) that stabilize the distorted structure. Following the recent work of Nori-Shargh and Weinhold, one observes that the orbitals involved in the vibronic coupling between the S₀/S_n states and those for the donor (filled)–acceptor (empty) interactions are identical. In fact, deletion of any particular pair of E²_{i → j} interaction creates vibrational instability in the buckled structure and as a corollary, deleting it for the planar structure removes its instability. The one-to-one correlation between the natural bond orbital theory and PJT theory assists in an intuitive identification of the relevant (few) excited states from a manifold of computed ones that cause symmetry breaking by vibronic coupling. © 2019 Wiley Periodicals, Inc.     

Taking into account physical and instrumental parameters in atomic absorption spectroscopy with a continuous radiation source

We present a detailed analysis of the dependences of the absorption contours and concentration curves on various parameters in atomic absorption spectrometry with a continuous radiation source. We have developed a multifunctional application software package allowing us to calculate the emission and absorption line profiles for different elements under different physical conditions. We take into account Doppler and collisional broadening of the absorption lines, which have a complex structure as a result of the isotopic shift, hyperfine splitting of the components, and also instrumental distortion of these lines. We consider two different procedures for calculating the absorbance and do a comparative analysis of the two procedures. For all the listed cases, we can plot concentration curves and find the absorbance within the classical definition and plot the concentration curve using only a portion of the spectral width of the profile rather than the entire width. We have modeled the instrumental distortions of the spectral profile due to spectral selection, and we have analyzed their effect on the shape of the absorption contour. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 3, pp. 285–289, May–June, 2006.     

On the nature of slow emission at 3.8 eV in crystalline α-Al2O3-δ

A comparative research of thermoluminescence, X-ray luminescence, and photoluminescence in initial and thermo-optically treated and X-ray irradiated anion-defective corundum (α-Al₂O_3-δ) samples has been carried out. A new type of center has been identified emitting near 3.6–3.8 eV up to 800 K, excited at 5.9 eV, and having a lifetime of about 300 ms at 300 K in the excited state. This type of centers was found to be created only at thermo-optical treatment, including ultraviolet irradiation with λ ≈ 280–320 nm and simultaneous heating of α-Al₂O_3-δ samples to 550–670 K, and be destructed thermally at T ≥ 670 K or when exposed to X-ray radiation or light with quantum energies of 5.9 and 3.1 eV. The center type found is assumed to have a complex structure consisting of interstitial aluminum, anion and cation vacancy, and slightly displaced regular ions in the nearest surrounding.     

Magneto-elastic effects in single-crystal USb0.8Te0.2

A high resolution X-ray diffraction study has been performed on a single crystal of USb_0.8Te_0.2. At room temperature this material has the cubic FCC (NaCl) structure. On cooling through the Néel point of 205 K USb_0.8Te_0.2 is known to enter a triple-q antiferromagnetic phase. Below T_C 175 K USb_0.8Te0.2 is a ferromagnet with net magnetisation along the 1 1 1 body diagonal. Four-circle X-ray scattering data from high-symmetry {h O h} and {h h h} reflections are presented as a function of temperature. We confirm that this magnetisation directly leads to a magneto-elastic distortion of the crystal lattice with a rhombohedral extension along the 1 1 1 body diagonals. At 130 K, this distortion is found to correspond to a rhombohedral bond angle of = 89.856° ± 0.004° consistent with previous results. In this single-crystal study we also present evidence for additional associated effects which we attribute to inter-grain stresses and sample mosaic structure.     

Identification of first- and second-order magnetic phase transitions in ferromagnetic perovskites

A criterion used for the determination of first- and second-order magnetic phase transitions from purely magnetic methods is applied to manganese perovskites of formula La_2/3(Ca_1−xSr_x)_1/3MnO₃. A crossover from first- to second-order character at a tolerance factor t=0.92 is found, which also brings about several variations in other physical properties. At t=0.92 a change from orthorhombic to rhombohedral symmetry also takes place. The impossibility of establishing static cooperative Jahn–Teller distortions in the rhombohedral symmetry is suggested as being responsible for the observed behaviour.     

A group theoretical study of f n systems in an environment of approximately icosahedral symmetry

Group theoretical methods are developed to determine in a generalised format for an f ⁿ ion in a crystal field environment of icosahedral symmetry, the effect on the energy level scheme when a crystal field distortion is considered parallel to any direction. As an illustration, the effect on the g-tensor components are examined as a function of the magnitude and the direction of the crystal field distortion. All appropriate reduced matrix elements in group theoretical terminology are evaluated for the f ⁿ -ion ground states. Specific results are given for the f ³-ion case and compared with electron paramagnetic resonance, optical, and magnetic susceptibility data.     

Representations and descriptors unifying the study of molecular and bulk systems

Establishing a unified framework for describing the structures of molecular and periodic systems is a long-standing challenge in physics, chemistry, and material science. With the rise of machine learning methods in these fields, there is a growing need for such a method. This perspective aims to discuss the development and use of three promising approaches—topological, atom-density, and symmetry-based—for the prediction and rationalization of physical, chemical, and mechanical properties of atomistic systems across different scales and compositions.     

Resonator insensitive investigation to thermal lens for end-pumped lasers

Optical pumping of solid-state lasers induces a thermal lens effect in the laser crystal; this thermal effect determines the beam properties. In this paper, the focal length of the thermal lens is calculated, and resonator parameter (g_1 g_2) is obtained, which is insensitive to thermal distortions when the product of the resonator parameters (g_1, g_2) equals 1/2. By using our calculated results, we get the fundamental transverse mode laser output with optic－optic conversion of 48.6%, and slope efficiency of 56.3%.