Molecular dynamics revealed from frequency dependent heat capacity

Temperature modulated DSC (TMDSC) measurements at reasonably high frequencies allow for the determination of baseline heat capacity. In this particular case vitrification and devitrification of the rigid amorphous fraction (RAF) can be directly observed. 0.01 Hz seems to be a reasonably high frequency for Bisphenol‐A Polycarbonate (PC). The RAF of PC is established during isothermal crystallization. Devitrification of the RAF seems to be related to the pre‐melting peak. For PC the melting of small crystals between the lamellae is thought to yield the pre‐melting peak.     

Evaluation of temperature integral for temperature dependent frequency factors

The general method of evaluating the temperature integral for temperature dependent frequency factors have been considered. The values of the temperature integral as evaluated by the present method are in excellent agreement with those obtained numerically.     

Simple derivation of the frequency dependent complex heat capacity

This paper gives a simple derivation of the well-known expression of the frequency dependent complex heat capacity in modulated temperature experiments. It aims at clarified again that the generalized calorimetric susceptibility is only due to the non-equilibrium behaviour occurring in the vicinity of thermodynamic equilibrium of slow internal degrees of freedom of a sample when the temperature oscillates at a well determined frequency.     

Temperature dependent structured absorption spectra of molecular chlorine

A dual wavelength range spectrometer system has been designed and constructed which can simultaneously perform single pass UV absorption spectroscopy and cavity enhanced absorption spectroscopy in the green region of the visible spectrum. Using the system the absorption spectrum of molecular chlorine has been measured, in the wavelength range 509-570 nm, using cavity enhanced absorption spectroscopy. Absolute absorption cross sections were obtained by simultaneous measurement of the UV spectrum to obtain the Cl(2) concentration. These are the first temperature dependent measurements of the Cl(2) absorption cross sections in this region which are vibronically resolved. Laboratory measurements were conducted at four temperatures (298, 273, 233, and 197 K). Spectral modelling of the Cl(2) B(3)Π(0(u)(+))-X(1)Σ(g)(+) electronic transition has been performed, the results of which are in good agreement with our measured spectra.     

Melting of orthorhombic betulin

Orthorhombic (s.g. P 2₁ 2₁ 2, a = 28.6145 Å, b = 27.4115 Å, c = 6.9536 Å, V = 5454.1 Å³) betulin (C₃₀H₅₀O₂) was found in this study to melt at 245 °C with the enthalpy of fusion 40.3 J mol^?1. The shape of the peak of melting gives rise to the belief that there are several polymorphs of betulin.     

Temperature dependent in situ doping of ALD ZnO

This study on ALD grown ZnO layers is aimed at the systematic study of the effect of incorporation of different Al contents on the properties of the layers. An alternate precursor pulse method was used for layer deposition. Optimal doping was achieved at 210 °C at 2 at% Al content. A relationship between crystalline morphology versus temperature and aluminium incorporation was established.     

Temperature dependence of solid uranyl-tris-acetate fluorescence spectra

Fluorescence spectra of Na [UO₂ acetate₃] measured at liquid nitrogen temperature are evaluated as the sum of vibronic transition bands, 8 base frequencies were found which build long progressions with the total-symmetric uranyl vibration. IR, FIR and Raman spectra were used to assign the vibrational bands.     

Temperature dependent energy transfer in Ar-O3 collisions

The energy transfer between argon atoms and ozone complexes O3*, excited in the region of the dissociation threshold, is calculated for fixed temperatures (100 K< or =T < or =2500 K) using classical trajectories. The internal energy of ozone is resolved in terms of vibrational and rotational energies. For all temperatures, energy flows from O3* to Ar. The vibrational energy transfer, relative to k(B)T, is very small below 500 K, but gradually increases towards high temperatures. The relative rotational energy transfer, on the other hand, monotonously decreases with T; around 1100 K it falls below the relative vibrational energy transfer. Thermally averaged cross sections for vibrational and rotational energy transfers are also calculated. The implications for the stabilization of ozone complexes in the energy transfer model are discussed.     

Temperature dependent dielectric relaxation study of ethylene glycol-water mixtures

Using the picosecond time domain reflectometry method, dielectric relaxation measurements for 13 ethylene glycol (EG)-water mixtures have been studied from 0 to 40°C. The dielectric relaxations in the mixtures show a Debye-type behavior, whereas the relaxation in pure EG can be described by the Cole-Cole model. The static dielectric constant ₀, the relaxation time and the dielectric constant at high frequency have also been determined at various temperatures. The dielectric relaxation data suggests that there is no tendency to form hydrogen bonds with the addition of water to EG unlike other alcoholic systems but this tendency becomes increasingly important with decreasing temperature. The activation energy decreases with increased water content in the mixture as expected.     

Temperature dependent optical absorption of partially polymerized diacetylene crystals

The temperature dependence of the absorption of diacetylene chains dispersed in partially polymerized monomer matrices has been measured over the range from 2 to 380 K for a number of different monomers. The results are interpreted in terms of the effects of the different lattice environments on the polymer chains. It is shown that, in general, the polymer chain length does not have a major effect on the absorption spectrum.     

Wavelength dependent photo-controlled differential release of compounds from solid phase resin

A method to effect photo-mediated differential release of bead-based compound libraries using a tuneable laser in combination with chromatically orthogonal photolabile linkers is described.     

单分散纳米InVO4(正交相)的低温合成

InVO₄ is a new developed visible light responding photocatalyst for water decomposition, which is obtained by a solid-state reaction at high temperature traditionally. In this paper, pure InVO₄ nano-crystalline powder has been prepared by a hydrothermal process at low temperature and was characterized by TEM, IR, and X-ray diffraction. Many factors such as pH value, reaction time and temperature have been investigated. It is found that the optimal conditions for the preparation is: n_InCl3∶n_NaVO3=1∶2; temperature : 150 ℃; Reaction time: 4～8 h; pH=7.9～8.0. And the experimental result shows that it is a convenient way to get single dispersing InVO₄ nano-crystalline powder by flux in alkyl alcohol.     

Static and frequency dependent polarizabilities and hyperpolarizabilities of H2Sn

The structure–polarization relationship was investigated in a series of polysulfanes, H₂S_n. The reported results demonstrate that the forms of change of the polarizability components, α_ii, and the second hyperpolarizability components, γ_iiii, as well as the average values α and γ, respectively, of H₂S_n with n are similar. This shows that polarizability components can be easily used to determine corresponding hyperpolarizability data. A remarkable change of the hyperpolarizabilities with the molecular geometry of H₂S_n was found. This result can be used for the design of nonlinear optical materials with optimum properties. The present study uses the flexible σ bonded H₂S_n and is complementary to the works that considered the effect of conformational changes of π-conjugated systems on their hyperpolarizabities. The present computations were performed using the semiempirical approaches MNDO and MNDO/d, as well as ab initio methods with STO-3G, extended with polarization and diffuse functions, and [3s2p/7s5p2d] sets for H₂S_n. At the ab initio level, the electronic and the vibrational contributions to polarizabilities and hyperpolarizabilities were both computed for several members of H₂S_n. The frequency dependence of the above contributions and the static limit were discussed. Electron correlation was taken into account for several test cases using MP2 theory. The selected methods and the variety of the approximations on which they rely allow the systematic consideration of the effect of changes of the geometry of H₂S_n on their polarizabilities and second hyperpolarizabilities. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 1698–1715, 1998     

Angular and frequency dependent spin relaxation study of liquid crystalline cyanobiphenyls

NMR field-cycling measurements of the Larmor frequency (v) and angular (Δ) dependences of the longitudinal proton spin relaxation time T₁ for the nematic liquid crystals 5CB and 8CB allow a more detailed analysis of the underlying molecular motions than data available previously. All T₁ (v, Δ) dispersion profiles essentially distinguish three frequency ranges where T₁ is governed by either local field effects, collective motions (director order fluctuations), or rotational and translational diffusion of individual molecules or molecular groups, respectively. The angular dependence supports and extends previous conclusions about the significance of the order fluctuation term at low (kHz) and high (MHz) Larmor frequencies; in addition it is the basis for the disentanglement of local field effects, which involve Jeener's dipolar relaxation, and of the sophisticated rotational relaxation models suggested in the literature by Dong, Nordio and Vold. It is found that Vold's third rate concept gives the best explanation of the measurements. The results on the rotational diffusion processes essentially agree with deuteron studies from the literature, but also reveal clear distinctions with regard to the anisotropy parameter σ, essentially due to the improved separation from the order fluctuation contribution.     

Temperature dependent positron annihilation studies in Nafion-117 polymer

We have measured the S-parameter and life-time as a function of temperature from 15 to 300 K in acid Nafion-117. In addition, high temperature measurements from 300 to 550 K have been carried out in acid as well as Cs neutralised Nafion membrane. The results are discussed.     

Temperature dependent charge distribution in three-dimensional homochiral cadmium camphorates

Three homochiral cadmium camphorates have been prepared through temperature-dependent synthesis; they form 3D homochiral networks without the crosslinking or pillaring functions of auxiliary neutral bipyridines and exhibit various degrees of charge separation associated with the degree of hydration and controllable by temperature.     

Temperature dependent solid-state proton migration in dimethylurea-oxalic acid complexes

The phenomenon of solid-state proton migration within molecular complexes containing short hydrogen bonds is investigated in two dimethylurea-oxalic acid complexes. Extensive characterisation by both X-ray and neutron diffraction shows that proton migration along the hydrogen bond can be induced in these complexes as a function of temperature. This emphasises the subtle features of the hydrogen bond potential well in such short hydrogen bonded complexes, both intrinsically and in the effect of the local crystalline environment. Based on these findings, the synthesis and analysis of a series of solid-state molecular complexes is shown to be a potential route to designing materials with tuneable proton migration effects.     

Temperature dependent study of rayleigh wing scattering in liquid acetonitrile

The results of a study on the temperature dependence of the Rayleigh wing scattering in liquid acetonitrile are presented. It was found that the relaxation times increase with rising temperature, a result which is in contradiction to the internal viscosity picture, which has been used to explain the high frequency wing scattering. However, a calculation utilizing a simple cell model of liquids produces results that are in reasonable agreement with experiment.