Stereodynamics study of reactions N(~2D)+HD→NH+D and ND+H

The product polarizations of the title reactions are investigated by employing the quasi-classical trajectory (QCT) method. The four generalized polarization-dependent differential cross-sections (PDDCSs) $({2\pi } / \sigma )(\d\sigma _{00} / \d\omega _t )$, $({2\pi } / \sigma )(\d\sigma _{20} / \d\omega _t )$, $({2\pi } / \sigma )(\d\sigma _{22 + } / \d\omega _t )$, and $({2\pi } / \sigma )(\d\sigma _{21 - } / \d\omega _t )$ are calculated in the centre-of-mass frame. The distribution of the angle between ${{\bm k}}$ and ${{\bm j^\prime }}$, $P(\theta _r )$, the distribution of the dihedral angle denoting ${{\bm k}}${--}$\bm k^\prime $--$\bm j^\prime $ correlation, $P(\phi _r )$, as well as the angular distribution of product rotational vectors in the form of polar plots $P(\theta _r ,\phi _r )$ are calculated. The isotope effect is also revealed and primarily attributed to the difference in mass factor between the two title reactions.     

Muon spin relaxation and susceptibility studies of the pure and diluted spin 1/2 kagomé-like lattice system (CuxZn(1-x))3V2O7(OH2) 2H2O

Muon spin relaxation and magnetic susceptibility measurements have been performed on the pure and diluted spin 1/2 kagomé system (CuxZn(1-x))3V2O7(OH)2 2H2O. In the pure x=1 system we found a slowing down of Cu spin fluctuations with decreasing temperature towards T approximately 1 K, followed by slow and nearly temperature-independent spin fluctuations persisting down to T=50 mK, indicative of quantum fluctuations. No indication of static spin freezing was detected in either of the pure (x=1.0) or diluted samples. The observed magnitude of fluctuating fields indicates that the slow spin fluctuations represent an intrinsic property of kagomé network rather than impurity spins.     

Isotopic effects of the N(2D) + H2 → NH + H reaction: a quantum time-dependent wave packet investigation

Based on the potential energy surface reported by Li and co-workers (J. Comput. Chem. 34 1686–1696 (2013)), the dynamics calculations of N(²D)?+?H₂(v ₀?=?0, j ₀?=?0) reaction and its isotopic variants HD and D₂ are studied using time-dependent wave packet method in the collision energy range of 0.01–1.0?eV. Dynamics properties such as reaction probability, differential cross section, and integral cross section are studied at state-to-state level of theory. Present values are compared with available theoretical and experimental results. The results indicate that the integral cross sections of N(²D)?+?D₂ reaction are in general good agreement with the experimental data at collision energy below 0.15?eV. The rotational state-resolved integral cross sections of N(²D)?+?H₂/HD/D₂ reactions are compared with experimental values for the first time, with the obtained values being in good agreement with the experimental data.     

Semiempirical valence bond potential energy surfaces for simple chemical reactions: 1 A′ states of H2O and H2F+

A semiemprical valence bond method is employed to study the potential energy surfaces (PESs) of the lowest ¹ A′ states of H₂O and isoelectronic H₂F⁺. The calculation is based on the search for the electronic configurations which play the most important rôle in the formation of the stable electronic states of the molecules and the relevant diatomic fragments. Several approximations are used to reduce the number of permutations in the calculation of the energy matrix. The Moffit atoms-in-molecule approximation is used to correct for the atomic errors arising from the poor basis set. The computed data for the lowest electronic states of OH, HF, HF⁺, H₂O and H₂F⁺, as well as the general behaviour of the PESs for different molecular geometries, are in good agreement with the available ab initio and experimental data.     

Stereodynamics of the reactions Ne＋H＋/Ne＋D2＋/Ne＋W2

The vector correlations between products and reagents for the reactions Ne＋H2＋, Ne＋D2＋, and Ne＋T2＋ are calculated by means of the quasi-classical trajectory method on a new potential energy surface constructed by Lfi et al, [J. Chem. Phys. 2010 132, 014303]. The polarization-dependent differential cross-sections （27π/σ）（dσ00/dωt）, （2π/σ）（dσ20/dwt）, （27π/σ）（dσ22＋/dwt）, and （2π/σ）（dσ21-/dwt）, and the distributions of P（θr）, P（φ）, and P（θr, Cr） are calculated. The isotopic effect, which is associated with the difference in mass factor among the three reactions, is revealed.     

Ion exchange studies of polycrystalline NA/K-β/β’-Al2O3 using XRF and neutron activation analysis

Neutron activation and X-ray fluorescent analysis were used to follow the ion exchange of polycrystalline (0.6 Na/0.4 K) Na/K- β/β”-Al₂O₃ in NaCl/KCl melts at 800°C and dilute acetic acid at 80°C. The results suggest that the material is not 0.6 Na-β”- Al₂O₃/0.4 K-β-Al₂O₃ but contains ⩽ 27% K⁺ in the β”-Al₂O₃ phase. The final hydronium exchanged material contains a substantial quantity of residual potassium.     

Influence of the reagent vibration on the stereo-dynamics of the reactions D^- ＋ H2 and H^- ＋ D2

Employing the quasi-classical trajectory method and the potential energy surface of Panda and Sathyamurhy [Panda A N and Sathyamurthy N 2004 J.Chem.Phys.121 9343],the effect of the reagent vibration on vector correlation of the ion-molecule reactions D～-+H₂ and H～-+D₂ is studied at a collision energy of 35.7 kcal/mol.Four generalized polarization-dependent differential cross sections （2π/σ）（dσ 00 /dωt）,（2π/σ）（dσ 20 /dωt）,（2π/σ）（dσ 22+ /dωt）,and （2π/σ）（dσ 21 /dωt） are presented in the centre-of-mass reference frame,separately.At the same time,the effects on the product angular distributions P （θr）,P （φr） and P （θr,φr） of the title reactions are also analysed.The calculated results show that the scattering tendencies of the product HD,the alignment and the orientation of j sensitively depend on reagent molecule vibration.     

Dynamical analysis of bounded and unbounded orbits in a generalized Hénon–Heiles system

The Hénon–Heiles potential was first proposed as a simplified version of the gravitational potential experimented by a star in the presence of a galactic center. Currently, this system is considered a paradigm in dynamical systems because despite its simplicity exhibits a very complex dynamical behavior. In the present paper, we perform a series expansion up to the fifth-order of a potential with axial and reflection symmetries, which after some transformations, leads to a generalized Hénon–Heiles potential. Such new system is analyzed qualitatively in both regimes of bounded and unbounded motion via the Poincaré sections method and plotting the exit basins. On the other hand, the quantitative analysis is performed through the Lyapunov exponents and the basin entropy, respectively. We find that in both regimes the chaoticity of the system decreases as long as the test particle energy gets far from the critical energy. Additionally, we may conclude that despite the inclusion of higher order terms in the series expansion, the new system shows wider zones of regularity (islands) than the ones present in the Hénon–Heiles system.     

Theoretical study of the O(1D) + H2(1Σ g +) reactive quenching process

Classical trajectory calculations have been made for the system O(¹ D) + H ₂(¹Σ _g ⁺) →OH(²Π) + H(² S) using an analytical singlet ground state surface for H ₂O. A rate constant of 1·73 × 10^-10 cm³ molecule^-1s^-1 at 300 K has been obtained. The distribution of energy in the products is approximately 30 per cent in translation, 45 per cent in vibration and 25 per cent in rotation. Because of the preponderance of vibrationally long-lived trajectories, statistical theories gave a good interpretation of the gross features of the reaction.     

Mechanism of solid-state oxidation of FeSO4·H2O: model of simultaneous reactions

The mechanism of the thermal transformation of FeSO₄·H₂O in air has been studied under isothermal conditions at temperatures (150–460)°C using mainly⁵⁷Fe Mössbauer spectroscopy and X-ray powder diffraction (XRD). Two trends are typical for the thermal behaviour of FeSO₄·H₂O in air, a tendency toward oxidation and dehydration. We suggested a new transformation model consisting of two ways of oxidation, direct one and indirect one. Fe(OH)SO₄ was identified as a product of the direct way, Fe₂(SO₄)₃ and superparamagnetic nanoparticles ofγ-Fe₂O₃ as products of the indirect way. The suggested model of simultaneous reactions explains the unusual non-monotonous dependence of the oxidation level of the thermally treated samples on temperature.     

Phase transition studies in CoSiF6·6H2O and Co1−xZnxSiF6·6H2O by Mn(II) EPR

Phase transition studies on single crystals of CoSiF₆·6H₂O and Co_1−xZn_xSiF₆·6H₂O (x = 0.082, 0.182, 0.248) using Mn(II) EPR at X-band were carried out in the temperature range 10–300 K. Phase transitions with considerable thermal hysteresis have been detected in CoSiF₆·6H₂O and Co_1−xZn_xSiF₆·OH₂O (x = 0.082, 0.182). In CoSiF₆·6H₂O, the transition temperatures during cooling (T^c_c) and during heating (T^h_c) were found to be considerably less than those obtained previously from magnetic anisotropy experiments, i.e. 230 and 246 K as against 246 and 259 K. These characteristic temperatures for the dilute crystals having x = 0.082 and 0.182 were 205, 218 K and 175, 185 K, respectively. It is thus evident that magnetic dilution with zinc causes a progressive reduction in the transition temperatures as well as in the thermal hysteresis. The phase transition manifests itself in a large discontinuous increase in the Mn(II) zero-field splitting parameter (D), i.e. from −187 ± 1 G to −290 ± 1 G, in these crystals. The hyperfine coefficient (A) also increases discontinuously from 99 ± 1 G to 102 ± 1 G at T_c. In the dilute crystal with x = 0.248 a very slow continuous decrease in D and practically no change in A have been detected with a lowering of the temperature. A small temperature independent positive g-shift (g = 2.020 ± 0.005) has been observed in all the crystals studied. The spin-lattice relaxation time (T₁) of the Co(II) ion in CoSiF₆·6H₂O at different temperatures, both above and below T_c, has been estimated from the observed Mn(II) hyperfine linewidth. A discontinuous change in T₁ at T_c has been observed. Analysis of the temperature dependence of the linewidth has further revealed that a two-level Orbach process describes well the thermal behaviour of the spin-lattice relaxation of the Co(II) ions in these crystals. The location of the first excited level in CoSiF₆·6H₂O determined from such studies at temperatures both above and below T_c has been examined in the light of the ligand field energy scheme of the Co(II) ion in an octahedral field. It is concluded that the phase transition in this crystal is probably accompanied by a change in sign of the axial field parameter (Δ).     

Dynamical analysis of fractional-order Rössler and modified Lorenz systems

This Letter is devoted to the dynamical analysis of fractional-order systems, namely the Rössler and a modified Lorenz system. The work here described compares the dynamical regimes of such fractional-order systems to that of the corresponding standard systems. It turns out that most of the chaotic attractors are topologically equivalent to those found in the original integer-order systems, although in some particular (and apparently rare) cases unusual bifurcation patterns and attractors are found.     

Crystal structure of the inverse weberite ZnFeF5(H2O)2, magnetic and mössbauer study of the antiferromagnet ZnFeF5(H2O)2 and ferrimagnet Mn FeF5(H2O)2

The room temperature crystal structure of the inverse weberite ZnFeF₅ (H₂O)₂ is refined from powder X-ray diffraction. The cell is orthorhombic (S.G. Imma, a = 7.475(1) →A, b = 10.766(1) →A, c = 6.594(1) →A, z = 4). Below T_N = 9(2) K, ZnFeF₅(H₂O)₂ becomes a 1-D antiferromagnet. This behaviour was characterized by susceptibility and magnetization measurements and Mössbauer spectroscopy. On the contrary, isotypic MnFeF₅(H₂O)₂ is confrimed to be a ferrimagnet below T_c = 39.5(1)K. Its magnetic and Mössbauer characteristics are, above and below T_c,and agree with a 3-D magnetic character. Ferrimagnetism could be due to frustration effects as in previously described Fe₂F₅(H₂O)₂.     

Infrared spectra of acetylene–water complexes: C2D2–H2O,C2D2–HDO,and C2D2–D2O

Infrared spectra of C₂D₂–water complexes are studied in the 4.1 μm region of the C₂D₂ ν₃ fundamental band using a tunable diode laser source to probe a pulsed supersonic slit jet. Relatively large vibrational red shifts (?27.7 to ?28.0 cm^?1) are observed which are more easily interpretable than for the analogous C₂H₂ vibration thanks to the absence of Fermi resonance effects for C₂D₂. Noticeable homogeneous line broadening leads to estimates of upper state predissociation lifetimes of about 0.5, 0.9 and 1.1 ns for C₂D₂–H₂O, –HDO, and –D₂O, respectively. Transitions involving K_a = 0 and 1 levels are observed for C₂D₂–HDO, but there is a puzzling absence of K_a = 1 for C₂D₂–H₂O and C₂D₂–D₂O.     

Stereodynamics of the reactions: F+H_2/HD/HT→FH+H/D/T

Among many kinds of ways to study the properties of atom and molecule collision, the quasi-classical trajectory(QCT) method is an effective one to investigate the molecular reaction dynamics. QCT calculations have been carried out to investigate the stereodynamics of the reactions F + H2/HD/HT→FH + H/D/T, which proceed on the lowest-lying electronic states of the FH2 system based on the potential energy surface(PES) of the 12A' FH2 ground state. Although the QCT method cannot describe all quantum effects in the process of the reaction, it has unique advantages when facing a three-atoms system or complicated polyatomic systems. Differential cross sections(DCSs) and three angle distribution functions P(θr), P(φr), P(θr, φr) on the PES at the collision of 2.74 kcal/mol have been investigated. The isotope effect becomes more obvious with the reagent molecule H2 turning into HD and HT. P(θr, φr), as the joint probability density function of both polar angles θr and φr, can reflect the properties of three-dimensional dynamic more intuitively.     

Mössbauer studies of PbFe2/3W1/3O3 multiferroics

Mössbauer studies of ceramic samples of the antiferromagnetic perovskite PbFe_2/3W_1/3O₃ have been carried out. It has been established that the temperature of transition to the magnetically ordered state is T _N = 365 K. Iron ions in PbFe_2/3W_1/3O₃ are found to reside in the high-spin Fe³⁺ state. The Fe³⁺ ions occupy inequivalent positions differing in the nearest cation environment, or more precisely, tungsten and iron ions are distributed in a random manner over the sites of the octahedral sublattice. The inequivalent positions arise as a result of the Fe and W ions being statistically distributed over the octahedral sublattice. For T > 0 K, magnetic fields at the nuclei and, hence, the average thermodynamic values of the magnetic moments of Fe³⁺ ions occupying inequivalent positions are different and, at a given temperature, are determined by the number of the nearest magnetic neighbors, with the effective magnetic fields (H _eff) varying differently with temperature. As the temperature is lowered, the fields H _eff level off gradually in response to the effective magnetic fields of iron ions having different numbers of exchange bonds leveling off with decreasing temperature which lowers thermal excitation.     

Collisional-Broadened and Dicke-Narrowed Lineshapes of H(2)(16)O and H(2)(18)O Transitions at 1.39 µm

We present results of a study on the self-broadening and broadening by nitrogen and oxygen of H(2)(16)O and H(2)(18)O lines in the 1.39-μm wavelength region using a distributed feedback semiconductor diode laser. To estimate the broadening coefficients, the absorption lineshapes were analyzed using the ordinary Voigt profile which provided good fits for most of the investigated lines. The broadening coefficients were found to be larger for nitrogen used as a perturber than for oxygen. This agrees with the fact that the quadrupole moment of N(2) is larger than that of O(2). Nevertheless, for lines involving high-rotational quantum number J, relatively smaller broadening coefficients were found and deviations of the measured profiles from the standard Voigt profile were observed. These deviations were ascribed as caused by Dicke-narrowing effect. Corresponding to this effect, collisional-broadening and narrowing coefficients were determined using the Nelkin-Ghatak profile which is suitable for the "hard"-collision model. The optical diffusion coefficients of the water in both nitrogen and oxygen gases were determined from the measurements of the collisional-narrowing coefficients. Copyright 2001 Academic Press.     

Dynamics and Cycle of Interstellar H2O and OH Masers

We present an improved radiative pumping model for interstellar H2O and OH masers.This oversomes the defects of former radiative models,and is compatible with astronomical conditions.For the regions of strong H2O and OH formation,it is shown that the rotational population is affected by collisions less than by radiation.A reasonable scheme for both regeneration and destruction of interstellar H2O and OH molecules is investigated.It can close the dynamical cycle of interstellar H2O and OH species,and can give an appropriate interpretation for both interstellar H2O and OH masers.This model has been confirmed by experiments.