Time Evolution of Vibration-Induced Excited State Decay

A simple model consisting of two electronic levels and one vibrational mode (phonon) was theoretically studied. The electronic-vibrational interaction was linear in the vibrational displacement. The vibrational mode was taken in the harmonic approximation and was attached to the thermal bath formed by the ambient environment. The kinetic constants of the vibrational dissipation were of the second order in the vibrational-bath coupling and were taken in the Markovian limit. Although, depending on the parameters of the model, different curves of the non-radiative vibration-induced excited state decay were obtained, in general, three time intervals, corresponding to different physical behaviour, were found. In the short-time interval, small oscillations superimposed on the excited state decay were observed. They were determined by the vibrational frequency and influenced by electronic-vibrational coupling. In the middle-time interval, almost quasi-exponential decay was detected; its rate constant increased with stronger electronic-vibrational interaction and speed of vibrational relaxation. In the long-time interval, the decay was very slow and, under special conditions, even an asymptotic non-zero excited state population was observed. Its value increased with the strength of the off-diagonal electron-vibrational coupling. Links of the parameters of the model with quantum chemical terms were estimated.     

Extraction-ability and -selectivity of tetra-aza-crown ethers for transition metal cations

In order to investigate the relative effects of the differences between the structures and lipophilicities of 1, 10-dioxa-4, 7, 13, 16-tetra-azacyclo-octadecane (TA-18-crown-6) and the tetrabenzyl derivative of 1,10-dioxa-4, 7, 13, 16-tetra-azacyclo-octadecane (TBTA-18-crown-6) on their extraction-abilities and -selectivities for transition metal cations, constants of the overall extraction (logK _ex) of 1:1 (M:L) complexes, the distribution (K _D) for two diluents (CH₂Cl₂ and CHCl₃) with different dielectric constants have been determined at 25 ± 0.1 °C. The magnitude of logK _ex is largely determined by that of K _D. The equilibrium constants of TA-18-crown-6 have been compared with those of TBTA-18-crown-6. It is found that:(i) logK _ex sequences of TA-18-crown-6 and TBTA-18-crown-6 for transition metals in CH₂Cl₂ lie in order: Fe³⁺ > Cu²⁺ > Mn²⁺ > Co²⁺ > Cd²⁺ > Ni²⁺ > Zn²⁺ and Fe³⁺ > Cu²⁺ > Co²⁺ > Mn²⁺ > Ni²⁺ > Cd²⁺ > Zn²⁺ respectively; (ii) the stability sequences of two types of tetra-aza-crown ethers with the transition metal cations in CHCl₃ are the same as follows: Fe³⁺ > Ni²⁺ > Cu²⁺ > Co²⁺ > Zn²⁺ > Cd²⁺ > Mn²⁺, and (iii) unusual selectivities are observed for transition metal-tetra-aza-crowns, e.g. the high Fe³⁺/M ⁿ⁺ selectivity factors (S_f) of TA-18-crown-6, except for the competitive-extractions for the special case in CHCl₃ of TBTA-18-crown-6, it was found that the Mn²⁺/M ⁿ⁺ values were relatively higher according to the other transition metal cations. A systematic sequence in these two types of solvents is not found for a given transition metal cation in terms of the variation of selectivity with the tetra-aza-crown ethers. The results provide alternatives for the rational design of other specific ligands on the transition metal cations.     

The kinetics of the light-induced defect creation in hydrogenated amorphous silicon – Stretched exponential relaxation

Our model for light-induced defect creation in hydrogenated amorphous silicon is applied to its kinetics, i.e., the growing curve of light-induced dangling bond density as a function of illumination time, which is fitted to a stretched exponential function. Two parameters β and τ involved in the function are estimated as functions of saturated dangling bond density in terms of our model. These are compared with two experimental results, i.e., our results obtained from ESR measurements and Shimakawa et al.’s results obtained from photoconductivity measurements. The saturated dangling bond density is also measured as a function of the generation rate of free carriers. The experimental results are compared with calculated results and discussed.     

On topological properties of the Hartman-Mycielski functor

We investigate some topological properties of a normal functorH introduced earlier by Radul which is some functorial compactification of the Hartman-Mycielski construction HM. We prove that the pair (H X, HMY) is homeomorphic to the pair (Q, σ) for each nondegenerated metrizable compactumX and each denseσ-compact subsetY.     

Planar Chromatography of Some 1-Arylpiperazines Behaving as Dopaminergic Ligands

JPC – Journal of Planar Chromatography – Modern TLC - The chromatographic behavior of fourteen 1-arylpiperazine derivatives has been studied by thin-layer chromatography on both silica...     

Transient binary nucleation from ethanol-hexanol vapour

We study condensation of ethanol-hexanol vapour by numerical solution of kinetic equations. The number of droplets formed in unit volume is computed within self-consistent classical model. It is shown that formation of ethanol-rich droplets prevails at the initial stage of nucleation process, but in the stationary state formation of droplets near the saddle point (on cluster formation energy surface) plays the dominant role. Presented at the 6th Joint Seminar “Development of Materials Science in Research and Education”, Karlštejn, Czech Republic, 17–19 September 1996. This work was supported by Grant No. A1010615 of the Grant Agency of the Academy of Sciences of the Czech Republic.     

Quadratic Functionals with General Boundary Conditions

The purpose of this paper is to give the Reid ``Roundabout Theorem' for quadratic functionals with general boundary conditions. In particular, we describe the so-called coupled point and regularity condition introduced in [16] in terms of Riccati equation solutions. Accepted 27 February 1996     

Quantum Interference, Quantum Theory of Measurement, and (In)completeness of Quantum Mechanics

The new techniques and ideas in quantum interferometry with neutrons, photons, atoms, electrons, and Bose condensates that fluorished in the last two decades have influenced in a decisive way the thinking and the research in the foundations and interpretation of quantum mechanics. The controversies existing among different schools on the reality of matter waves of quantum theory, the postulates of quantum measurement theory, and the (in)completeness of quantum mechanics have to be approached now in a new way. Our argumentation follows the spirit of the Paris school.