Spin solitons in molecular magnetic materials with the chiral structure

Quasiperiodic sequences of the maxima of microwave absorption with decreasing amplitudes have been observed in a temperature range of 4–50 K in the electron spin resonance spectra of ferrimagnetic chiral single crystals [Mn{(R/S)-pn}]₂[Mn{(R/S)-pn}₂(H₂O)][Cr(CN)₆]₂, as well as [Cr(CN)₆][Mn(S)-pnH-(H₂O)]H₂O. Theoretical estimates and previous experimental data indicate that the Dzyaloshinskii-Moriya interaction is the main factor determining the chirality of the spin density and the existence of soliton solutions for the spin dynamics in these crystals. The experimental dependences obtained for the distances between the microwave power absorption maxima on the constant component of the magnetic field of the spectrometer correspond to the theoretical predictions for spin solitons in three-dimensional magnetic materials and exhibit another behavior in crystals with quasi-two-dimensional magnetic ordering.     

Spin solitons and waves in chiral molecular ferrimagnets

Resonance modes corresponding to a spin-soliton resonance have been found in the electron spin resonance spectra of [Cr(CN)₆][Mn(S)-pnH-(H₂O)]H₂O two-dimensional (2D) chiral single crystals and [Mn{(R/S)-pn}]₂[Mn{(R/S)-pn}₂(H₂O)][Cr(CN)₆]₂ chiral single crystals with a 3D magnetic order. It is also established that the chiral crystals of both types exhibit a spin-wave resonance analogous to the excitation of standing spin waves in thin magnetic films. At the same time, racemic crystals of the first type do not exhibit spin-soliton resonance. The entire body of experimental data indicates that the chirality of crystals influences the spin excitations (standing spin waves and solitons) in these media.     

Hyperfine anomaly arising from the nuclear spin-forbidden transition,and absolute sign determination of the zero-field splitting constant

It has been found in the triplet E.S.R. spectra of radical pairs in irradiated potassium deuterium fumarate that the hyperfine structure of the two transitions, M _s = 1?0 and M _s = 0?+1, are entirely different. This anomaly has been interpreted in terms of the forbidden transition arising from the mixing of the nuclear spin states by the anisotropic hyperfine interaction. The theory has been developed for multiplet electron spin systems and includes the nuclear Zeeman interaction which is often neglected. The theoretical predictions are in good agreement with the observed separations and intensities of the anomalous hyperfine lines. In addition, it has been found that since the forbidden lines of the electron spin multiplet system with S ≥ 1 appear strongly only in transitions which include some specific electronic spin states, the anomalous features of the spectra make it possible to determine the absolute sign of the zero-field or hyperfine splitting constant, if the sign for one of them is known. Using this principle, attempts have been made to determine the absolute sign of the zero-field splitting constant for a number of triplet E.S.R. spectra which exhibit a hyperfine anomaly arising from the proposed mechanism.     

Dipole-coupled carbon-13 spectra,a source of structural information on liquid crystals

It is shown that the introduction of well-selected dipolar interactions into carbon-13 spin systems of liquid crystals can lead to well-resolved spectra with a rich content of structural information. Two possibilities are investigated: (a) selective isotope substitution, in particular by deuterium and nitrogen-15, and simultaneous proton decoupling; (b) two-dimensional separated local field carbon-13 spectroscopy. The methods are demonstrated by investigations of benzylidene anilines in their nematic phases.     

Enhancement of optical nonlinearity in a guest-host system by nematic ordering

Second-harmonic generation (SHG) has been studied for understanding the enhancement mechanism for the second-order optical nonlinearity by the nematic (or axial) ordering in a liquid crystal doped with one-dimensional nonlinear optical (NLO) organic molecules. An extended version of the Maier-Saupe mean-field theory for nematic liquid crystals was developed to obtain analytical expressions for the second-order NLO coefficients in terms of the axial order, the polar order and the effective nematic potential. From the SHG data in a guest-host system composed ofN,N'-dimethylaminonitrostilbene molecules (0.5% by weight) and a liquid crystal, the enhancement of the second-order NLO coefficient,d ₃₃, by nematic ordering becomes almost 3, which agrees well with our theoretical predictions.     

A determination of zeeman parameters for NO2 in its ground state

Extensive measurements of magnetic dipole transitions in the gas phase E.P.R. spectrum of NO₂ in its [Xtilde] ² A ₁ state are reported. This type of transition was first identified by Burch, Tanttila and Mizushima. The data have been fitted simultaneously with measurements from the far infra-red laser magnetic resonance spectrum of NO₂ to determine the principal components of the electron spin g-tensor. The results are consistent with Curl's relationship between the components of the electron spin and spin-rotation tensors. It is necessary to include the effects of centrifugal distortion of the spin-rotation interaction and two parameters describing this interaction are determined in the course of the analysis. Some discussion of the origins of these parameters is included.     

On the centrifugal distortion in the microwave spectra of O2 and SO

Stable radicals formed by room temperature X-irradiation of single crystals of acridine and phenazine have been identified and their structures determined by detailed ENDOR studies at 77 K. The E.S.R. spectra are of little assistance in the identification of these radicals. However, the high resolution of ENDOR has made it possible to study all the proton hyperfine interactions in detail. The radicals investigated in this study are formed as a result of the addition of atomic hydrogen to the nitrogen atom of the acridine and phenazine molecules. ENDOR lines of all the protons have been identified and analysed. Spin densities have been deduced from the proton hyperfine tensors. Although the unpaired electron is extensively delocalized throughout the molecule, there are large spin densities (0·475 and 0·584, respectively) on C₉ in acridine and the second nitrogen in phenazine. Excellent agreement has been obtained between the observed spin densities and those computed by INDO molecular orbital calculations. The design and construction of a simple rectangular ENDOR cavity operating in the TE₁₀₁ mode is described.     

Electron-spin resonance and theoretical studies of radicals formed from trimethylamine borane : the radicals Me2[Ndot]-BH3 and (Me3N-BH3)-

Exposure of trimethylamine borane to ⁶⁰Co γ-rays at 77 K gave, initially, a four-line E.S.R. spectrum assigned to the radical anion, Me₃[Ndot]-BH₃ ^-, having a large (58 G) hyperfine coupling to boron. Theoretical calculations suggest that the radical resembles a perturbed ^.BH₃ ^- in which the normally planar unit still has considerable pyramidal character.

After annealing above 77 K this species was lost and a multiline, isotropic spectrum grew in which, by comparison with spectra obtained from Me₃N-BD₃, is shown to belong to Me₂[Ndot]-BH₃ radicals. This species is of interest because of the large ¹H coupling to the -BH₃ protons (ca. 45 G). This coupling, qualitatively ascribed to hyperconjugation, is correctly reproduced by theoretical (ab initio UHF) calculations.     

Orientational order parameter studies in two symmetric dimeric liquid crystals – an optical study

The optical technique developed by [W. Kuczynski, B. Zywucki, and J. Malecki, Determination of orientational order parameter in various liquid-crystalline phases, Mol. Cryst. Liq. Cryst. 381 (2002), pp. 1–19; B.J. Zywucki and W. Kuczynski, IEEE transactions on optical phenomena – The orientational order in nematic liquid crystals from birefringence measurements, Dielectr. Electr. Insul. 8 (2001), pp. 512–515] is fabricated and used to determine the orientational order parameter in two dimeric liquid crystalline compounds nematic and SmA phases of α,ω-bis(4-alkylanilinebenzylidene-4′-oxy)alkane (m.OnO.m) homologous series. The compounds studied are 5.O8O.5 and 5.O10O.5 which exhibit nematic and SmA, and nematic phases, respectively. The orientational order parameter in both the phases of nematic and SmA phases of the compound one and the nematic phase of the compound two are obtained using the principle of Newton's rings which gives directly the birefringence, δn of the liquid crystal dimer. The merits of the technique used are presented over the conventional techniques for the determination of orientational order parameter. The results for the two compounds are compared with those values estimated from n _e, n _o and density using the two internal field models due to Vuks and Neugebauer applicable to nematic phase.     

Threshold effect of microwave power on ferromagnetic resonance in K<Subscript>0.4</Subscript>[Cr(CN)<Subscript>6</Subscript>][Mn(S)-pn](S)-pnH<Subscript>0.6</Subscript> single crystals

A stepwise change in the ferromagnetic resonance spectrum in a K_0.4[Cr(CN)₆][Mn(S)-pn](S)-pnH_0.6 chiral magnet has been observed in a critical microwave magnetic field of 1.8 Oe. The threshold changes in the ferromagnetic resonance spectra are caused by Suhl instability leading to the generation of defects of the magnetic structure, chiral spin solitons. The threshold effect is not observed in the same microwave range in similar chiral crystals [Cr(CN)₆][Mn(S)-pnH(H₂O)](H₂O) with a stronger Heisenberg exchange interaction.     

Relation between orientational order parameters of matrix and probe in nematic liquid crystals

Summary The phenomenological relation between the orientational order parameters of matrix (S) and probe (S _p) has been obtained and confirmed for a large number of impure nematic liquid cyrstals. The temperature-dependent parts of the parametersS andS _p are proportional to one another and have the same critical behaviour over the whole mesophase range, although the absolute values ofS andS _p as well as their temperature dependencesS(T) andS _p(T) may be sufficiently different. The relation observed is not the consequence of the known molecular-statistical theories of impure nematic liquid crystals. Work presented at the second USSR-Italy Bilateral Meeting on Liquid Crystals held in Moscow, September 15–21, 1988.     

A comparison between the radicals formed by radiation in barbituric acid and its 2-thio derivative

The radicals formed by radiation in 2-thiobarbituric acid single crystals have been studied by E.S.R. spectroscopy. The main radical is formed by abstraction of one of the protons bonded to C₅. The electronic structure of this radical has been compared to that of the related radical formed in ordinary barbituric acid. Both the experimental data as well as the MO calculations show that when oxygen is substituted by sulphur the isotropic proton splitting is reduced and the g-value anisotropy increased. This is explained by a transfer of unpaired spin density from C₅ to the sulphur atom.     

Macroscopic behavior of non-polar tetrahedratic nematic liquid crystals

We discuss the symmetry properties and the macroscopic behavior of a nematic liquid crystal phase with D_2d symmetry. Such a phase is a prime candidate for nematic phases made from banana-shaped molecules where the usual quadrupolar order coexists with octupolar (tetrahedratic) order. The resulting nematic phase is nonpolar. While this phase could resemble the classic D _∞h nematic in the polarizing microscope, it has many static as well as reversible and irreversible properties unknown to nonpolar nematics without octupolar order. In particular, there is a linear gradient term in the free energy that selects parity leading to ambidextrously helical ground states when the molecules are achiral. In addition, there are static and irreversible coupling terms of a type only met otherwise in macroscopically chiral liquid crystals, e.g. the ambidextrous analogues of Lehmann-type effects known from cholesteric liquid crystals. We also discuss the role of hydrodynamic rotations about the nematic director. For example, we show how strong external fields could alter the D_2d symmetry, and describe the non-hydrodynamic aspects of the dynamics, if the two order structures, the nematic and the tetrahedratic one, rotate relative to each other. Finally, we discuss certain nonlinear aspects of the dynamics related to the non-commutativity of three-dimensional finite rotations as well as other structural nonlinear hydrodynamic effects.     

Excimer emission from tetrachloro-p-xylene

The E.S.R. spectrum of vanadyl acetylacetonate dissolved in a liquid crystal which is nematic at room temperature has been investigated. The spectrum differs from other E.S.R. studies in liquid crystals with nematic ranges at elevated temperatures in that the molecular tumbling time has slowed enough to produce a ‘glassy’ type spectrum. Previous theories are no longer applicable and a method is discussed for determining the degree of order from the relative intensities of the parallel and perpendicular components of the hyperfine spectrum. The method is supported by the drastic change in intensities upon application of a transverse electric field.     

A Fe[Nb]-Li center in stoichiometric LiNbO<Subscript>3</Subscript> crystals: Mechanism of formation

A new iron center in stoichiometric lithium niobate crystals has been studied by the EPR method. The angular dependences of the EPR spectrum of the center have been used to derive the parameters of its spin Hamiltonian. The data amassed on the variation in the concentrations of two iron centers in lithium niobate crystals annealed in a Li₂CO₃ powder have provided an insight into the mechanism of formation of the new center, as well as corroborated its model proposed by us earlier. According to this model, the center represents a complex of two defects aligned with the polar axis in the crystal: the iron ion at the niobium site and an interstitial lithium ion filling the nearest structural vacancy (Fe³⁺[Nb]-Li⁺[V]). The structure of other Fe³⁺ centers revealed earlier in LiNbO₃ crystals, in which the iron ion occupies the niobium site, has been discussed.     

N.M.R. study of the 125Te shielding anisotropy of tellurophene dissolved in various nematic liquid crystals

The ¹²⁵Te N.M.R. spectrum of tellurophene in three liquid crystals was recorded and analysed. The different orientational behaviour of tellurophene in the liquid crystals enabled the anisotropy of the tellurium-125 shielding tensor, σ _zz - 1/2(σ _xx + σ _yy ), and the difference σ _xx - σ _yy of the tensor elements to be determined. The resulting values are -1569 ± 21 ppm and 307 ± 26 ppm, respectively. The analysis of the ¹²⁵Te N.M.R. spectra is also discussed.     

Effect of deuteration on the electronic and electron-vibrational properties of the organic conductor k-(D8-BEDT-TTF)2[Hg(SCN)2Br]

We present here for the first time polarized reflection spectra and optical conductivity spectra of single crystals of the newly deuterated organic conductor k-(D₈-BEDT-TTF)₂[Hg(SCN)₂Br] at room temperature. The spectral region investigated is 700–40 000 cm⁻¹. We examined the effect of deuteration on electronic and electron-vibrational transitions observed in the spectra. The observed shift of the electron “dimer” transition in the infrared toward lower frequencies upon deuteration is linked with an increase in the interaction between neighboring, mutually perpendicular dimers in the structure of the deuterated crystal. A lowering of the symmetry of the BEDT-TTF molecule is demonstrated in crystals similar to k-(BEDT-TTF)₂[Hg(SCN)₂Br], relative to the symmetry D _2h of the free molecule. We refine the assignment of the spectral features determined by the interaction of electrons with the fully-symmetric intramolecular vibrations of the C=C, C-S, and C-C-H bonds of the BEDT-TTF molecule. Fiz. Tverd. Tela (St. Petersburg) 40, 1595–1598 (September 1998)     

热致液晶CPHOB的有序参数与核磁共振弛豫

从室温至380K测量了热致液晶4-己氧基苯甲酸4-氰基苯酯（CPHOB）的氢核磁共振谱．其固态至向列相的转变温度T_sn=347K，向列相至各向同性液体的转变温度T_ni=359K．得到了液晶态有序参数的温度关系．讨论了氢核磁共振的自旋晶格弛豫机制． 关键词：     

A time resolved photo-CIDEP study of electron transfer in durosemiquinone radicals

The time dependent E.S.R. spectra of the duroquinone anion radical, DQ^-, produced by laser flash photolysis, are studied in detail and shown to be quantitatively consistent with previous theoretical predictions. It is established that the degenerate electron transfer reaction between DQ^- and its parent molecule is an important spin relaxation mechanism in this radical and that it has a profound effect on the form of the experimental E.S.R. time profiles.