Nonadiabatic sudden increase of the cooperative kinetic effect at lattice energy stabilization—Microscopic mechanism of superconducting state transition: Model study of MgB2

The theory of the nonadiabatic electron–vibration interactions has been applied to the study of MgB₂ superconducting state transition. It has been shown that at nonadiabatic conditions in which the Born–Oppenheimer approximation is not valid and electronic motion is dependent not only on the nuclear coordinates but also on the nuclear momenta, the fermionic ground‐state energy of the studied system can be stabilized by nonadiabatic electron–phonon interactions at broken translation symmetry. Moreover, the new arising state is geometrically degenerate; i.e., there are an infinite number of different nuclear configurations with the same fermionic ground‐state energy. The model study of MgB₂ yields results that are in a good agreement with the experimental data. For distorted lattice, with 0.016 Å/atom of in‐plane out‐of‐phase B? B atoms displacements out of the equilibrium (E_2g phonon mode) when the nonadiabatic interactions are most effective, it has been calculated that the new arising state is 87 meV/unit cell more stable than the equilibrium–high symmetry clumped nuclear structure at the level of the Born–Oppenheimer approximation. The calculated T_c is 39.5 K. The resulting density of states exhibits two‐peak character, in full agreement with the tunneling spectra. The peaks are at ±4 meV, corresponding to the change of the π band density of states, and at ±7.6 meV, corresponding to the σ band. The superconducting state transition can be characterized as a nonadiabatic sudden increase of the cooperative kinetic effect at lattice energy stabilization (NASICKELES). © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Vibronic dressed electronic states and nonadiabatic effects in polyacetylene

Conditions for low and high T_c superconductors following from the nonadiabatic electron-vibrational theory at ab initio level have been obtained. According to the presented results, the supercurrent is realized by the motion of the ground-state electronic-charge distribution of the fully occupied band. The motion of the electronic-charge distribution is conditioned by the newly arisen, nondissipative degrees of freedom of nuclear, Jahn–Teller-like, microflows. The Meissner effect is also interpreted.     

Sodium and silver phosphate glasses doped with chlorides of Fe,Mn and Zn

A number of samples of sodium and silver phosphate glasses doped with various compositions of some transition metals viz. iron, manganese and zinc chlorides alongwith undoped samples of sodium and silver phosphate glasses were synthesized and characterized by X-ray diffraction, IR spectral, electrical conductivity and differential scanning calorimetry (DSC). The glass transition temperature (T _g) and crystallization temperature (T _c) values obtained from DSC curves were found to increase with increasing concentration of the dopant Fe/Mn/Zn chlorides in both sodium and silver phosphate glasses and the following sequence is observed: T _g(–FeCl₃)>T _g(–MnCl₂)>T _g(–ZnCl₂) T _c(–FeCl₃)>T _c(–MnCl₂)>T _c(–ZnCl₂) The increase in T _g and T _c values indicate enhanced chemical durability of the doped glasses. The electrical conductivity values and the results of FTIR spectral studies have been correlated with the structural changes in the glass matrix by the addition of different transition metal cations as dopants.     

Absorption UV spectroscopy and electronic structure of ionic and tautomeric forms of hydroxy and methoxy derivatives of cytosine and adenine,and of some 5-substituted analogs of pyrimidines

The individual absorption spectra of various ionic and tautomeric species of some derivatives of nucleic-acid components have been determined by computer handling of the summary spectra of these compounds measured at different pH values. These individual spectra have been decomposed into separate bands represented by log-normal curves and corresponding to different electronic transitions. Using the parameter system calculated earlier for the molecules of the vitamin B₆ family, the calculation of the electronic spectra and electronic structure of various ionic and tautomeric species of the molecules studied have been carried out in the π-electron approximation. These properties have also been calculated by the all-valence electronic method CNDOS . The calculated results correlate well with both approximations and with our experimental spectral data. The localization of the molecular electronic excitation studied on the transition to the S₁ and T₁ states is considered in connection with the reactivity in these states.     

DSC studies on sodium phosphate glasses doped with chlorides of Cd,Co and Ag

A number of samples of sodium phosphate glasses doped with Cd/Co or Ag chlorides were prepared and characterized by X-ray diffraction, IR spectral, ion transport and DSC studies. It was found from DSC studies that the glass transition temperature (T _g) and crystallization temperature (T _c) values increased with the increasing concentrations of the dopants Cd/ or Co chlorides. However, the T _g and T _c values were found to decrease when the AgCl was taken as the dopant and the following sequence is observed: T _g(CoCl₂)>T _g(CdCl₂)> T _g(AgCl) T _c(CoCl₂)>T _c(CdCl₂)>T _c(AgCl) These results have been discussed and explained on the basis of changes in the structure of sodium phosphate glassy matrix by the addition of different cations as dopants.The authors are thankful to Prof. M. L. Srivastava, Head, Department of Chemistry, D. D. U. Gorakhpur University, Gorakhpur, and Prof. Suresh Chandra, Department of Physics, B. H. U. Varanasi for providing necessary laboratory facilities and help in carrying out the present work. The financial support from the Department of Science and Technology and University Grants Commission, New Delhi is also gratefully acknowledged.     

Crossover in dynamics of polymeric liquids: Back to Tll?

Light scattering spectra of two polymers, polyisobutylene (PIB) and polystyrene (PS), were analyzed in the broad frequency range at temperatures above the glass transition (T_g ). At high temperatures, the spectra followed the qualitative scenario suggested by mode‐coupling theory (MCT) of the glass transition. The crossover temperature (T_c ) was defined to be approximately 1.35 T_g in PIB and approximately 1.15 T_g in PS. At lower temperatures (T < T_c ), the light scattering spectra deviated strongly from the idealized MCT scenario. Different signs of the dynamic transition around T_c are discussed. The difference between the suggested interpretation and an old idea of the liquid–liquid transition in polymeric liquids is stressed: we describe the transition as purely dynamic in nature. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2785–2790, 2000     

聚对苯二甲酸乙二酯非晶区反式构象结构的探讨

<正> 聚对苯二甲酸乙二酯(PET)的重复单元中有乙撑基。它的碳碳键内旋转产生反式构象(T)和左右式构象(G)。用其不同的构象来表征PET的聚集态结构,对研究结构与性能的关系是十分重要的。许多工作都已指出,乙撑基反式构象的谱带热处理时随结晶度的增加而增加。X-射线衍射的结果证实     

Comments on a paper by Axelson and Mandelkern concerning 13C NMR spectra of polymers

It is shown that the ¹³C NMR spectral collapse temperatures T_c reported by Axelson and Mandelkern tend to give a constant ratio of T_c/T_g averaging 1.21 ± 0.05 and independent of T_g or of polymer structure. It is further shown that T_c is not a high-frequency value for T_g because this would require T_c/T_g to decline with increasing T_g. T_c/T_g agrees in numerical value with T_u/T_g, where T_ll is the liquid-liquid transition lying above T_g. Direct comparison of T_c and T_u for four polymers PIB, PnBA, atactic PP, and isotactic PMMA shows very close agreement. The various results suggest, but do not prove, that T_c from ¹³C NMR spectroscopy may be a new, direct measure for T_ll. A measured T_c of 233K for linear PE is compatible with a T_g near 195 K (233/195 = 1.19), whereas a T_g of 148 K gives the ratio 233/148 = 1.57, which is outside any value shown in tabulated form.     

Spectroscopic evidence for triplet excitation energy transfer among carotenoids in the LH2 complex from photosynthetic bacterium <Emphasis Type="Italic">Rhodopseudomonas palustris</Emphasis>

The LH2 complex from Rhodopsudomonas (Rps.) palustris is unique in the heterogeneous carotenoid compositions. The dynamics of triplet excited state Carotenoids (³Car* has been investigated by means of sub-microsecond time-resolved absorption spectroscopy both at physiological temperature (295 K) and at cryogenic temperature (77K). Broad and asymmetric T _n ←T ₁ transient absorption was observed at room temperature following the photo-excitation of Car at 532 nm, which suggests the contribution from various carotenoid compositions having different numbers of conjugated C=C double bonds (N_c=c). The triplet absorption bands of different carotenoids, which superimposed at room temperature, could be clearly distinguished upon decreasing the temperature down to 77 K. At room temperature the shorter-wavelength side of the main T_n04T₁ absorption band decayed rapidly to reach a spectral equilibration with a characteristic time constant of ∽1 μs, the same spectral dynamics, however, was not observed at 77 K. The aforementioned spectral dynamics can be explained in terms of the triplet-excitation transfer among heterogeneous carotenoid compositions. Global spectral analysis was applied to the time-resolved spectra at room temperature, which revealed two spectral components peaked at 545 and 565 nm, and assignable to the T_n04 T₁ absorption of Cars with Nc=c=11 and Nc=c=13, respectively. Surprisingly, the decay time constant of a shorter-conjugated Car, i.e. 0.72 ώs (aerobic) and 1.36 ώs (anaerobic), is smaller than that of a longer-conjugated Car, i.e. 2.12 us (aerobic) and 3.75 ώs (anaerobic), which is contradictory to the general rule of carotenoids and relative polyenes. The results are explained in terms of triplet-excitation transfer among different types of Cars. It is postulated that two Cars with different conjugation lengths coexist in an α, β-subunit in the LH2 complex.     

A generalised perturbation-based equation of state for thermodynamic modelling of fluids over a wide range of density

A new generalized perturbed thermodynamic nonlinear isotherm regularity (GPTNLIR) equation of state (EoS) has been proposed for the fluids over the entire density range from gas to liquid. The GPTNLIR has been derived on the basis of an effective nearest neighbor pair interaction of an extended average effective pair potential (AEPP) in the framework of the thermodynamic perturbation theory (TPT). The selected AEPP is an extended Lennard-Jones (12, 6, 3) type which considers the repulsive, dispersion, dipole-dipole and longer-range interactions between pair molecules, respectively. Based on the EoS, a non-linear relationship exists between (Z– Z_CS)v² and ρ for each isotherm of fluid, where Zis the compression factor, v=1/ρis the molar volume, Z_CS is Carnahan–Starling (CS) expression for the compression factor of the reference fluid with the temperature-dependent effective hard-core diameter (σ_eff). The validity of EoS against the experimental p–v–Tdata were tested for a variety of fluids, including polar, non-polar, hydrogen bonded and quantum fluids. This EoS provides the estimation of σ_eff at T>T_c, T=T_c and T<T_c, in which T_c is critical temperature, for each real fluid using its experimental p–v–T data and the extension of TPT theory as well.     

Solvent crazing of “dry” polystyrene and “dry” crazing of plasticized polystyrene

The critical strain ε_c for crazing of polystyrene in each of a variety of organic liquids has been measured along with the degree of swelling of the polymer by the liquid and the attendant reduction in the glass transition temperature T_g of the polymer. The critical strain for the crazing in air and the T_g of each of a set of specimens molded from mixtures of o-dichlorobenzene and polystyrene have also been determined. Correlations of ε_c with T_g in the two cases are identical within experimental error for the first 40°C of T_g reduction; these results imply (1) that organic liquids do not exercise a significant surface energy role in solvent crazing and (2) that their only roles are associated with flow processes. Correlation of solvent crazing ε_c with solubility parameter of the crazing fluid is very poor for several reasons that are discussed.     

A multi-dimensional microcanonical Monte Carlo study of S0 → T1 intersystem crossing of isocyanic acid

A general formula for the multi-dimensional Monte Carlo microcanonical nonadiabatic rate constant expressed in configuration space is applied to calculate the rate of intersystem crossing (ISC) between the ground (S₀) and first excited triplet (T₁) states for isocyanic acid. One-, two- and three-dimensional potential energy surfaces are constructed by coupled-cluster single-double CCSD calculations, which are used for Monte Carlo sampling. The calculated S₀→T₁ ISC rate is in good agreement with experimental findings, which gives us a reason to believe that the multi-dimensional Monte Carlo microcanonical nonadiabatic rate theory is a very effective method for calculating nonadiabatic transition rate of a polyatomic molecule.     

Photoisomerization of cis‐1,2‐di(1‐Methyl‐2‐naphthyl)ethene at 77 K in Glassy Media

cis‐1,2‐Di(1‐methyl‐2‐naphthyl)ethene, c‐ 1,1 , undergoes photoisomerization in methylcyclohexane, isopentane and diethyl ether/isopentane/ethanol glasses at 77 K. On 313 nm excitation the fluorescence of c‐ 1,1 is replaced by fluorescence from t‐ 1,1 . Singular value decomposition reveals that the spectral matrices behave as two component systems suggesting conversion of a stable c‐ 1,1 conformer to a stable t‐ 1,1 conformer. However, the fluorescence spectra are λ_exc dependent. Analysis of global spectral matrices shows that c‐ 1,1 is a mixture of two conformers, each of which gives one of four known t‐ 1,1 conformers. The λ_exc dependence of the c‐ 1,1 fluorescence spectrum is barely discernible. Structure assignments to the resolved fluorescence spectra are based on the principle of least motion and on calculated geometries, energy differences and spectra of the conformers. The relative shift of the c‐ 1,1 conformer spectra is consistent with the shift of the calculated absorption spectra. The calculated structure of the most stable conformer of c‐ 1,1 agrees well with the X‐ray crystal structure. Due to large deviations of the naphthyl groups from the ethenic plane in the conformers of both c‐ and t‐ 1,1 isomers, minimal motion of these bulky substituents accomplishes cis → trans interconversion by rotation about the central bond.     

The phase behaviour ofl-α-phosphatidylcholine in the presence of chlorpromazine under different experimental conditions

The phase behaviour ofl-α-phosphatidylcholine liposomes has been studied as a function of temperature, pH, ionic strength, etc., in the presence and absence of chlorpromazine by a polarization method using 1,6-diphenyl-1,3,5-hexatriene as a fluorescence probe. The gel crystalline to liquid crystalline (T_c), liquid crystalline to cubic (T_II), and cubic to hexagonal (H_II) transition temperatures in multilayer liposomes have been detected, and are found to be affected by chlorpromazine under different experimental conditions.     

Comparative IR spectroscopic study of phosphorus-containing dendrimers built of thiophosphoryl, cyclophosphazene and phthalocyanine cores

The FTIR spectra of four generations of phosphorus-containing dendrimers built of thiophosphoryl, cyclophosphazene and phthalocyanine cores with terminal benzaldehyde and P–Cl groups have been recorded and analyzed. FT-Raman spectra of four generations of phosphorus dendrimers built of cyclotriphosphazene core with terminal benzaldehyde groups have been detected. Their spectral pattern is determined by the ratio T_n/R_n (T_n—number of terminal groups, R_n—number of repeating units). This ratio trends to r − 1 (r—branching functionality of repeating unit), and becomes constant, when the generation number is higher than 3. Experimental IR spectra of dendrimers built of thiophosphoryl, cyclophosphazene and phthalocyanine cores are very closely similar. The dependence of band full width at half height in IR spectra on the number of dendrons is established. The possibility appears to separate the bands assigned to the core, repeating units and terminal groups of dendrimers by difference spectroscopy method.     

Melting behavior of isotactic polystyrene

The melting behavior of isotactic polystyrene, crystallized from the melt and from dilute solutions in trans-decalin, has been studied by differential scanning calorimetry and solubility measurements. The melting curves show 1, 2, or 3 melting endotherms. At large supercooling, crystallization from the melt produces a small melting endotherm just above the crystallization temperature T_c. This peak originates from secondary crystallization of melt trapped within the spherulites. The next melting endotherm is related to the normal primary crystallization process. Its peak temperature increases linearly with T_c, yielding an extrapolated value for the equilibrium melting temperature T_c° of 242 ± 1°C as found before. By self-seeding, crystallization from the melt could be performed at much higher temperature to obtain melting temperatures as high as 243°C, giving rise to doubt about the value of T_c° found by extrapolation. For normal values of T_c and heating rate, an extra endotherm appears on the melting curve. Its peak temperature is the same for both melt-crystallized and solution-crystallized samples, and independent of T_c, but rises with decreasing heating rate. From the effects of heating rate and partial scanning on the ratio of peak areas and of previous heat treatment on dissolution temperature, it is concluded that this peak arises from the second one by continuous melting and recrystallization during the scan.     

Cold crystallization and thermal shrinkage of uniaxially drawn poly(ethylene 2,6-naphthalate) by solid-state coextrusion

Solid-state coextrusion has been used to prepare uniaxially drawn films from isotropic poly(ethylene 2,6-naphthalate) (PEN) of a minimum degree of crystallinity (ca. 5%) both below and above its glass transition temperature T_g. The onset of cold crystallization (T_c) of the drawn films has been studied as a function of the extrusion temperature (ET) and the draw ratio (EDR). It has been shown that T_c decreases markedly on draw, as much as 95°C, and, at constant draw ratio T_c goes through a minimum in the T_g region. For undrawn PEN, annealing below 153°C has no significant effect on T_c. To evaluate the crystallization rate constant (k) and the activation energy (E_a) of the drawn specimens, a nonisothermal DSC procedure has been used. With increasing EDR, k increases markedly and E_a goes down over threefold compared with the undrawn polymer. At high ET, strain-induced crystallization has also been shown to play an important role in lowering E_a for cold crystallization. Thermal shrinkage above T_m indicates a high elastic recovery, underlining the efficiency of deformation, ca. 93%, achieved by solid-state coextrusion.     

Nonadiabatic collision model calculations of ion-pair formation cross sections of Cs+O2→Cs++O

This paper has improved Hickman's nonadiabatic collision model by substituting Hickman's constant velocity classical straight line trajectory approximation with the solution of motion equation mR=?dV(R)/dR, and has calculated the cross sections of ion-pair formation Cs+O₂→Cs⁺+O^?₂ with the improved nonadiabatic collision model (INCM). A comparison of our results with other theoretical and experimental results has been made.     

Critical Behavior of {Water + AOT + Decane} Microemulsion with Small Molar Ratio of Water to AOT

The coexistence curves of (T,n), (T,φ) and (T,ψ) (n,φ,ψ are the refractive index, the volume fraction, and the effective volume fraction, respectively) for a ternary microemulsion system of {water + sodium di(2-ethylhexyl) sulfosuccinate (AOT) + n-decane} with the molar ratio 25.1 of water to AOT have been determined at constant pressure within about 7 K from the critical temperature T _c by measurements of refractive index. The critical exponent β has been deduced from the (T,n), (T,φ) and (T,ψ) coexistence curves within 1 K above T _c . They were 0.323, 0.327, and 0.329, respectively, and were consistent with the 3D-Ising value. Furthermore, the experimental results have been analyzed to obtain critical amplitudes B and the Wegner-correction terms B ₁, to examine the diameters of the coexistence curves and to discuss the goodness of density variables for constructing order parameters.     

Equilibrium thermal behavior and morphology of organophilic montmorillonite/poly(ε‐caprolactone) nanocomposites

With differential scanning calorimetry, we have demonstrated a peculiar behavior under equilibrium conditions of neat poly(ε‐caprolactone) and its organophilic montmorillonite nanocomposites. In particular, in the determination of the equilibrium melting temperature by the extrapolation of the data of the melting temperature (T_m) versus the crystallization temperature (T_c), a bimodal trend has been observed. At the lower T_c's, the data of T_m follow a constant trend, whereas at the higher ones, the usual increasing trend has been obtained. Morphological observations by atomic force microscopy (AFM) have provided evidence of two different crystalline morphologies for the lower and higher T_c ranges. Moreover, AFM has shown that the thermal treatments strongly influence the clay dispersion in the polymer matrix. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 22–32, 2006