Particular features of incorporation of coumarin 30 into nanoparticles from metal complexes and the intensity of its columinescence

We have studied the sensitized fluorescence of coumarin 30 incorporated into nanoparticles from complexes of p-phenylbenzoyltrifluoroacetone and 1,10-phenanthroline with Y, La, Lu, Gd, Al, and Sc ions in 10% alcoholic-aqueous solutions. We have shown that, upon formation of nanoparticles from complexes of Y(III) and Ln(III) ions, coumarin 30 molecules are completely incorporated from the solution into nanoparticles from complexes up to dye concentrations in the solution comparable with the concentration complexes. For the nanoparticles under study, in the whole range of the examined dye concentrations, concentration quenching of the coumarin 30 cofluorescence has not been observed. Our results show that coumarin 30 is incorporated into lanthanide and yttrium complexes as a synergistic bidentate ligand. The possibility of creating brightly luminescent markers that absorb not only in the range of 360?C370 nm, but also in the range of 440?C450 nm, and have a narrow fluorescence spectrum with ??_max = 520 nm has been demonstrated.     

Energy migration toward a dye in nanoparticles from complexes with short fluorescent state lifetimes

We have studied regular features of the fluorescence sensitization (cofluorescence) of coumarin 30 and rhodamine 6G introduced into nanoparticles from complexes Ln(PhBTA)₃phen, where PhBTA is p-phenylbenzoyltrifluoroacetone and Ln is a triply charged Pr, Nd, Sm, Eu, Er, or Yb ion, which absorbs in the fluorescence range of ligands of complexes and dyes. We show that both the cofluorescence intensities (I _cofl) of rhodamine 6G in nanoparticles from Sm and Eu complexes and the behavior of intensity I _cofl on the content of rhodamine 6G coincide with the corresponding data obtained for nanoparticles from La and Lu complexes doped with rhodamine 6G molecules. A considerable decrease in I _cofl of rhodamine 6G is observed only in nanoparticles from complexes Nd(PhBTA)₃phen. In nanoparticles from Pr, Nd, Sm, Eu, Er, and Yb complexes doped with coumarin 30, it has been observed that, depending on the choice of the central ion, I _cofl of coumarin 30 is 2 to 80 times lower compared to I _cofl of the dye in nanoparticles from La and Lu complexes. A separate analysis of the influence of these ions on the energy transfer from complexes to coumarin 30 and on the fluorescence intensity of coumarin 30 incorporated into nanoparticles from these ions showed that a decrease in I _cofl of coumarin 30 by a factor of 2?C20 occurs due to the reduction of ??_fl of ligands of complexes under the influence of the interaction with Pr, Nd, Sm, Eu, Er, and Yb ions. Since ??_fl of complexes La(PhBTA)3phen is ??2 ps, while that of complexes Gd(PhBTA)3phen is ??1 ps, then, in nanoparticles with a maximal decrease in I _cofl of coumarin 30, ??_fl of complexes is reduced to ??0.1 ps. It has been found that, in nanoparticles from complexes with this ??_fl, energy migration over complexes takes place. However, as distinct from nanoparticles from La, Lu, and Y complexes, the free path length of singlet excitons in nanoparticles from complexes of absorbing ions is smaller than the nanoparticle size.     

Sigma trans promotion effect in transition metal complexes: a manifestation of the composite nature of binding energy

It is well known that intra-fragment electronic reorganization is one among several important components of the binding energy (bond dissociation energy) for two fragments forming an adduct. An interesting manifestation of this notion is proposed: a counterintuitive trend in binding energies that shall be commonly observed for a series of particular open shell transition metal containing complexes binding a small molecule at an empty coordination site. The prediction is that stronger σ interaction between the metal and the ligand trans to the empty site will result in a larger magnitude of binding energy and, possibly, a lower substrate coordination barrier. This trend, which we call the ‘trans promotion effect’ (TPE), is exemplified with a case study of dinitrogen binding by tri- and four-coordinated Mo(III) complexes. It is demonstrated that a trans amine ligand significantly increases the magnitude of dinitrogen binding energy. Orbital analysis and decomposition of the binding energy show that substrate coordination is favoured by stronger interaction of Mo with the trans ligand due to the d_z2 orbital of Mo that is occupied in the complex but vacant in the dinitrogen adduct.     

Tungsten cluster migration on nanoparticles: minimum energy pathway and migration mechanism

Saddle point searches have been employed to investigate the migration mechanisms of W clusters on W nanoparticles, and to determine the corresponding migration energies for the possible migration paths of these clusters. The tungsten clusters containing up to four adatoms are found to prefer 2D-compact structures with relatively low binding energies. The effect of interface and vertex regions on the migration behavior of the clusters is significantly strong, as compared to that of nanoparticle size. The migration mechanisms are quite different when the clusters are located at the center of the nanoparticle and near the interface or vertex areas. Near the interfaces and vertex areas, the substrate atoms tend to participate in the migration processes of the clusters, and can join the adatoms to form a larger cluster or lead to the dissociation of a cluster via the exchange mechanism, which results in the adatom crossing the facets. The lowest energy paths are used to be determined the energy barriers for W cluster migrations (from 1- to 4-atoms) on the facets, edges and vertex regions. The calculated energy barriers for the trimers suggest that the concerted migration is more probable than the successive jumping of a single adatom in the clusters. In addition, it of interest to note that the dimer shearing is a dominant migration mechanism for the tetramer, but needs to overcome a relatively higher migration energy than other clusters.     

Sensitization of fluorescence of dye molecules in nanoparticles of metal complexes

We studied the dependence of absorption and fluorescence spectra of complexes of Al, In, Sc, Y, and La with dibenzoylmethane and naphthoyltrifluoroacetone, as well as the dependence of sensitized fluorescence of dyes in nanoparticles of these complexes, in relation to the water pH, the ratio between ions and diketones, and the ion selection. We showed that the ability of complexes of ions to form nanoparticles that efficiently sensitize dye molecules incorporated into them is determined by stability constants of these ions with organic ligands and by their ability to compete with the formation of hydroxy complexes of these ions. We found that nanoparticles consist of diketonates of different compositions and that Nile red incorporated into nanoparticles is an indicator of the dependence of the composition of nanoparticles on the selection of the central ion of complexes and conditions of their formation. We revealed that complexes M(diketone)(OH)₂ self-assemble into nanoparticles with an admixture of dye molecules and efficiently sensitize dyes upon excitation into absorption bands of complexes. We showed that, at concentrations of rhodamine 6G in water smaller than 50 nM, the use of a solution that contains 50 μM of Al(III), In(III), or Sc(III) + 50 μM of naphthoyltrifluoroacetone makes it possible to increase the sensitivity of the luminescence analysis by 20-fold for the presence of rhodamine 6G in an aqueous solution.     

Quantum theory of impurity migration in crystals

A quantum theory of impurity migration in crystals is proposed. The impurity state is taken in the form of a wave packet constructed out of its Bloch states in the host lattice. Its time evolution is studied including its interaction with the host lattice phonons. A correspondence is established between the classical diffusion equation and the time evolution of the probability density arising out of the impurity wave packet. The diffusion coefficient D_T and trapping rate γ_T are related to the imaginary part of the energy shift of the impurity caused by its interaction with phonons. The detailed calculations are carried out using second order perturbation theory for the energy shift. The Debye model for the host lattice and effective mass approximation for the impurity band are used. At low temperature D_T is found to be proportional to_T3/2, and at high temperature the Arrhenius formula of Vineyard is obtained. The estimated migration energy for μ⁺ migration in bcc metals agrees reasonably with the experimental values.     

Spectral and luminescent properties of coumarins in nanoparticles from metal ion complexes

We have studied the absorption spectra of complexes of trivalent ions Y, La, Lu, and Sc with p-phenylbenzoyltrifluoroacetone that were introduced into a solution of 90% H₂O + 10% iso-C₃H₇OH in the absence and presence of either 1,10-phenanthroline or coumarins 6, 7, or 30. We have shown that these coumarins, as well as phenanthroline, are synergistic bidentate ligands that are incorporated into complexes up to concentrations comparable with concentrations of complexes and that stabilize them in the solution. We have studied the dependences of the fluorescence (cofluorescence) intensity (I _cofl) of the coumarins on their concentration in nanoparticles from the complexes mentioned above. We have shown that, in nanoparticles from complexes of Y(III), Ln(III), and Sc(III), I _cofl of coumarin 30 at high concentrations is higher than I _cofl of coumarins 6 and 7. In addition, up to concentrations of coumarin 30 comparable with the concentration of complexes in nanoparticles, there is no concentration quenching of its fluorescence. For coumarins 6 and 7, which are prone to association in the solution under study, the process of incorporating coumarins into complexes competes with their association, which leads to concentration quenching and changes in the shape of their cofluorescence spectra.     

An energy band calculation of linear chain transition metal complexes

The energy band structure of a class of linear chain compounds is investigated using a modification of the Green's Function Method. A discussion of the implications of the band structure to the properties of compounds in this class is presented.     

Photofield migration and desorption of impurity ions

Models which permit the theoretical study of diffusion-like processes under the simultaneous application of a pulsed laser field and a spatially nonuniform, quasiconstant electric field are proposed. The mean rates of photofield desorption are found. Evaluations show that it is comparatively easy to observe these effects experimentally and that they can find application in solving various problems in nanotechnologies. Zh. Tekh. Fiz. 67, 59–61 (December 1997)     

Role of kinematic factors in the manifestation of CO and CC vibrations in β-diketonate metal complexes

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 54, No. 5, pp. 736–739, May, 1991.     

闪锌矿GaN量子点中类氢杂质态的束缚能

在有效质量近似下,用变分法研究了闪锌矿GaN/AlxGa1-xN单量子点中的类氢杂质态。结果表明量子点中的杂质位置和量子点结构参数（量子点高度H、半径R及Al含量x）对施主束缚能有很大的影响。当杂质位于量子点中心时,施主束缚能 有最大值。此外,施主束缚能 随着量子点高度H（半径 ）的增大而减小,随着量子点中Al含量x的增大而增大。     

Properties of a magnetic impurity in a metal

The effect of a polarized conduction-electron cloud back on a magnetic impurity dissolved in a metal is studied. It is shown that at a temperature T _c much higher than the Kondo temperature the system becomes unstable against symmetry breaking and that a state with 〈S _z 〉 ≠ 0 is established. The behavior of 〈 S _z 〉 is derived for all temperatures and magnetic fields except for a very narrow region around T _c and for very low temperatures. The minute role of Kondo-type processes in establishing the symmetry-broken state is pointed out. Pis’ma Zh. éksp. Teor. Fiz. 66, No. 3, 184–189 (10 August 1997) Published in English in the original Russian journal. Edited by Steve Torstveit.     

Size dependence of the surface energy and surface tension of metal nanoparticles

The specific surface energy of small nanoclusters of transition fcc metals is calculated using the many-particle tight-binding potential and its earlier analog, the Gupta potential. The calculations are performed using both a theoretical model and computer simulations based on the Monte Carlo method. The equimolecular surface is considered as the dividing surface. It is found that at short radii of the nanoclusters, the surface energy and surface tension grow linearly as the particle radius increases. The values of the coefficient of proportionality in the dependence of the specific surface energy on the radius of a nanocluster are compared to the available literature data, experimental and otherwise.     

Binding energy of hydrogenic impurity in multi-quantum-dot structure

In this paper, we perform a theoretical study, using a variational method, of the binding energy of ground state for hydrogenic impurity in the multi-quantum-dot structure. It is found that the binding energy is not only as a function of the size of the system in the x–y plane, but also the barrier thickness and the width of a dot in the z direction. Especially, when the barrier thickness is equal to the width of a dot, there are two peaks in the behavior of the binding energy as a function of the barrier thickness. All these behaviors of the binding energy are determined by the competition between the localization effect of the wave function and the tunneling effect of the wave function due to an increase or decrease in the barrier thickness and the width of a dot. Moreover, we also investigate the behavior of binding energy with different impurity position.     

Particular features of fluorescence of jet-cooled vapor of 2,3-diazabicyclooctene

The fluorescence and fluorescence excitation spectra of azocompound, 2,3-diazabicyclo[2.2.2]oct-2-ene, have been studied using jet cooling. The violation of the mirror symmetry between the fluorescence and fluorescence excitation spectra due to an intense long-wavelength emission that manifests itself in solutions and in the gas phase cannot be eliminated even by jet cooling. It has been revealed that the bands of pure electronic and vibronic transitions are split by 0.55 cm^?1, which is caused by tunneling with accompanying emission from an intermediate short-lived state and which may be the reason for the violation of the mirror symmetry of the spectra upon tunnel inversion.     

金属/掺杂聚合物/金属结构中载流子的注入与输运

基于紧束缚的Su-Schrieffer-Heeger模型，利用非绝热的动力学方法，研究了金属/聚合物/金属三明治结构中载流子注入与输运的动力学过程，其中，聚合物中含有一个掺杂离子. 电子波函数随时间的演化满足含时Schrdinger方程，晶格运动满足经典的牛顿运动方程. 研究发现，掺杂离子对注入到聚合物中的载流子的作用类似一个控制阀门，阀门的状态与电场的强度和偏压的大小密切相关.     

金属/掺杂聚合物/金属结构中载流子的注入与输运

基于紧束缚的Su-Schrieffer-Heeger模型,利用非绝热的动力学方法,研究了金属/聚合物/金属三明治结构中载流子注入与输运的动力学过程,其中,聚合物中含有一个掺杂离子. 电子波函数随时间的演化满足含时Schrdinger方程,晶格运动满足经典的牛顿运动方程. 研究发现,掺杂离子对注入到聚合物中的载流子的作用类似一个控制阀门,阀门的状态与电场的强度和偏压的大小密切相关. 关键词： 载流子输运 波包 非绝热动力学     

Particular features of the acoustic wave propagation in condensed media in different conditions

The light spectrum of molecular scattering is used for studying the particular features of the hypersound propagation in a guaiacol—glycerol binary solution with two critical points. The kinetics of the spectrum of scattered light in liquid salol is studied when the viscosity of the latter varies over ten orders of magnitude. Acoustic singularities are revealed in the critical region at the phase transition and at a large viscosity.     

Particular features of a Vavilov-Cherenkov-like phenomenon with emission of surface plasmons

We consider a phenomenon of the Vavilov-Cherenkov type that can be observed in a space with a metal-dielectric boundary that well reflects light. An electron that initially uniformly moves at a constant velocity near this boundary creates surface plasmon-polaritons the phase velocity of which is lower than the electron velocity. The momentum of a photon in the created plasmon-polariton is calculated. This momentum may be almost as high as the doubled initial electron momentum. The velocity of the electron that created the photon in the plasmon-polariton may also become almost zero. We show that, at a nonzero temperature, this process has a nonzero probability.