Quantum-Chemical Calculations of the Excited Electronic States of the Prodan Molecule and Its Complexes in Water

A quantum-chemical calculation of the prodan molecule and its complexes in water for the geometry of the ground and fluorescent states is carried out. To describe the fluorescent state, changes in the electronic state (population) on bonds and atoms during transition of the molecule into an excited state are taken into account. A model of interaction of the prodan molecule with a polar proton-donor solvent (water) is suggested. It is shown that interaction with the ionic forms (H₃O₊ provides an explanation for the sensitivity of prodan to the solvent (displacement of the fluorescence bands). The nature of the electronic excited states of the prodan molecule and its complexes has been investigated. The constants of the rates of radiative and nonradiative processes and the fluorescence quantum yields have been calculated. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 3, pp. 330–334, May–June, 2005.     

Complexing and quenching of the prodan fluorescence

Experimental and quantum-chemical investigations of the prodan molecule are carried out. Prodan complexes in binary mixtures with nitromethane are investigated. Models of prodan-nitromethane interactions of both NN and NB bond types are constructed. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 5, pp. 59–64, May, 2006.     

Temporal dependences of dipole moments of prodan molecules

The fluorescence spectra of 6-propyl-2-dimethylaminonaphtalene (prodan), 1-(phenylamino)naphthalene (1-PAN), and 3-aminophthalimide are measured in glycerol with a picosecond resolution. The instantaneous fluorescence spectra and the correlation functions of the time-dependent Stokes shift of the fluorescence spectra of the two latter probes are used to find the time dependence of the dielectric response function of glycerol, which is necessary for calculating the charge transfer kinetics in prodan molecules. Based on the solvatochromism theory and using the experimental dependences of the time-dependent shift of the fluorescence bands for prodan molecules, which are characterized by efficient charge transfer in the excited electronic state, the kinetics of the electric dipole moment of the first singlet state is calculated.     

Effect of energy transfer on the kinetics of the decay and anisotropy of luminescence of prodan molecules

The temporal characteristics of the decay and polarization of luminescence of prodan solutions with different concentrations, excited by a picosecond laser radiation, are studied. The kinetics of the emission decay and polarization depend on the spectral range of luminescence recording and on the luminophore concentration and reflect the relaxation processes (leading to a long-wavelength shift of the entire emission band) and, in the case of sufficiently high concentrations, nonradiative energy transfer between the prodan molecules. It was found that the evolution of luminescence anisotropy in a diluted solution depends on the recording wavelength, which allowed us to calculate the average times of the Brownian rotational diffusion for prodan in glycerol, whose maxima were determined to be about 40 ns in the spectral region near 520 nm and to decrease to 14 and 17 ns at the edges of the emission region at 450 and 560 nm, respectively.     

Effect of proton-donor solvent and structural flexibility of prodan and laurdan molecules on their spectral-luminescent properties

The influence of structural flexibility on dipole moments, energy-level locations, and charge distributions in prodan and laurdan molecules was studied. A quantum-chemical calculation of isolated prodan and laurdan molecules in the fluorescent state geometry was conducted. Rate constants for radiative and non-radiative processes and fluorescence quantum yields for these probe molecules were calculated. Interaction centers of prodan and laurdan with a proton-donor solvent were estimated quantitatively. The possibility of using fluorescent probes for estimating the polarity of proton-donor and proton-acceptor solvents was shown. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 3, pp. 334–341, May–June, 2009.     

Nonradiative energy transfer in a concentrated solution of prodan

The temporal characteristics of luminescence decay in concentrated solutions of prodan excited by picosecond laser radiation are studied The electronic spectra exhibit a strong inhomogeneity, which, in the case of elevated solution viscosity, manifests itself under steady-state conditions of measurements. The temporal characteristics of the luminescence decay and the time-resolved luminescence spectra point to the occurrence of relaxation processes causing a long-wavelength shift of the emission band with time. An increase in the prodan concentration from 10^?4 to 5 × 10^?2 M leads to a faster increase in the luminescence lifetime in the long-wavelength spectral region and to a higher rate of shifting of the instantaneous spectra, which is related to energy transfer over the states of inhomogeneous broadening of the luminophore.     

Theoretical study of the chemisorption of H2 on boron cluster surfaces

“Ab initio” RHF calculations are used to investigate the chemisorption of a H₂ molecule on boron cluster surfaces. Potential energy surfaces and electron charge difference density plots are given. The results obtained indicate that the H₂ molecule in certain cases is dissociated on the surface, and that the hydrogen atoms are individually bound to different boron atoms. It is also found that the chemisorbed hydrogen atoms can move almost freely in certain directions parallel to the boron surface.     

Encapsulation of methane molecules into carbon nanotubes

Methane gas (CH₄) is a chemical compound comprising a carbon atom surrounded by four hydrogen atoms, and carbon nanotubes have been proposed as possible molecular containers for the storage of such gases. In this paper, we investigate the interaction energy between a CH₄ molecule and a carbon nanotube using two different models for the CH₄ molecule, the first discrete and the second continuous. In the first model, we consider the total interaction as the sum of the individual interactions between each atom of the molecule and the nanotube. We first determine the interaction energy by assuming that the carbon atom and one of the hydrogen atoms lie on the axis of the tube with the other three hydrogen atoms offset from the axis. Symmetry is assumed with regard to the arrangement of the three hydrogen atoms surrounding the carbon atom on the axis. We then rotate the atomic position into 100 discrete orientations and determine the average interaction energy from all orientations. In the second model, we approximate the CH₄ molecule by assuming that the four hydrogen atoms are smeared over a spherical surface of a certain radius with the carbon atom located at the center of the sphere. The total interaction energy between the CH₄ molecule and the carbon nanotube for this model is calculated as the sum of the individual interaction energies between both the carbon atom and the spherical surface and the carbon nanotube. These models are analyzed to determine the dimensions of the particular nanotubes which will readily suck-up CH₄ molecules. Our results determine the minimum and maximum interaction energies required for CH₄ encapsulation in different tube sizes, and establish the second model of the CH₄ molecule as a simple and elegant model which might be exploited for other problems.     

Adsorption of water molecule on (001) and (110) surfaces of MgH2

First principle calculations have been performed to explore the adsorption characteristics of water molecule on (001) and (110) surfaces of magnesium hydride. The stable adsorption configurations of water molecule on the surfaces of MgH₂ were identified by comparing the total energies of different adsorption states. The (110) surface shows a higher reactivity with H₂O molecule owing to the larger adsorption energy than the (001) surface, and the adsorption mechanisms of water molecule on the two surfaces were clarified from electronic structures. For both (001) and (110) surface adsorptions, the O p orbitals overlapped with the Mg s and p orbitals leading to interactions between O and Mg atoms and weakening the O–H bonds in water molecule. Due to the difference of the bonding strength between O and Mg atoms in the (001) and (110) surfaces, the adsorption energies and configurations of water molecule on the two surfaces are significantly different.     

Ergodic properties of the multidimensional rayleigh gas with a semipermeable barrier

We consider a multidimensional system consisting of a particle of massM and radiusr (molecule), surrounded by an infinite ideal gas of point particles of massm (atoms). The molecule is confined to the unit ball and interacts with its boundary (barrier) via elastic collision, while the atoms are not affected by the boundary. We obtain convergence to equilibrium for the molecule from almost every initial distribution on its position and velocity. Furthermore, we prove that the infinite composite system of the molecule and the atoms is Bernoulli.     

Inhomogeneous spectral broadening and the decay kinetics of the luminescence spectra of prodan

The selectively excited steady-state luminescence spectra, as well as the decay time characteristics of the luminescence, of prodan in polar solvents excited by picosecond radiation are studied. The steady-state luminescence spectra exhibit a strong inhomogeneous broadening, which is the most pronounced at elevated solution viscosities. The temporal characteristics of the luminescence decay in different spectral ranges and the instantaneous spectra suggest the presence of relaxation processes resulting in a long-wavelength shift of the emission spectrum during the lifetime of the excited state. A relation between the relaxation shift of the emission spectrum and the intermolecular orientational relaxation of solvate molecules is established.     

Molecular dynamics simulation of HCl in liquid Ar

Molecular dynamics simulations of one HCl molecule in liquid Ar at three different thermodynamic states have been carried out. The dynamic properties of both the solute molecule and solvent atoms are discussed. Results for Ar in the first solvation shell of HCl are compared with those for atoms in the bulk. The study includes radial distribution functions, residence times, velocity autocorrelation functions, spectral densities, self - diffusion coefficients, reorientational time correlation functions and infrared spectra.     

Calculation of the Parameters of the Dimeric Association of Water Molecules and Determination of Their Temperature Dependence

The conditions are determined, and the parameters for the onset of the mode of dimeric molecular association in the water system are estimated. The characteristics of dimeric associates of molecules are determined. The region of anomalous thermal compression water is increased from T ≤ 4°C to T ≤ 66.4°C by introducing the temperature equivalent T₀ of the energy of proton transition from molecule to molecule into the parameter of resonant interaction of atoms of different molecules. The time of transfer of excitation energy correlates with the periods of the valence and deformation vibrations of the molecules. Therefore, a molecule that performs valence vibrations “has time” to store an excitation energy sufficient to provide a parallel orientation of the spins of the nuclei of the hydrogen atoms in the molecules. Molecules that perform deformation vibrations have zero spins because of the smallness of the frequencies of such vibrations.     

The structure and bonding of furan on Pd(111)

The structure and bonding of molecular furan, C₄H₄O, on Pd(111) has been investigated using density functional theory (DFT) calculations and the results compared with those of a recent experimental investigation using scanned-energy mode photoelectron diffraction (PhD). The DFT results confirm the orientation of the molecular plane to be essentially parallel to the surface and show a clear energetic preference for one of the two possible structures identified in the PhD study, namely that with the molecule centred over the hollow sites of the surface. Two slightly different geometries at the hollow sites are found to be essentially energetically equivalent; in both cases, one Pd surface atom bonds to two C atoms, while two other Pd atoms each bond to one C atom. These structures differ in that in one case the pair of C atoms bonding to a single Pd atom are both β-C (C atoms not bonded to O in the furan molecule), whereas in the second case this pair of C atoms comprises one β-C and one α-C (adjacent to the O atom in furan). In both structures the C–Pd bonding is accompanied by displacements of the H and O atoms away from the surface and out of the molecular plane and local C–Pd coordination consistent with a rehybridisation of the C bonding to sp³ character.     

Ti原子在Al(110)表面吸氢过程中催化作用的第一性原理研究

运用第一性原理方法对H₂分子在Ti掺杂和纯的Al(110)表面的吸附情况进行了研究,发现有Ti原子掺杂时,存在一个H₂分子的吸附路径,即位于Al(110)面顶位Ti原子上方的H₂分子会发生解离,并与Ti原子形成TiH₂分子,然后TiH₂分子向能量更低的空位移动并接近Al(110)表面.态密度与电荷布居分析显示,吸附完成后H原子与表面Al原子存在较强的共价键作用,这为Al-H类物质及Na_{3 关键词： 钛 吸附 解离能 第一性原理}     

Proposing an efficient algorithm for designing universal nanoelectronic molecular logic gates

In today's world, there are still demands for minimising the dimensions of electronic circuits, the result of which is designing nanoelectronic circuits and very small molecular gates and switches. The point which causes trouble in this design is high impact of different parameters on the performance of circuit. Despite the suggestion of simple electronic circuits and different gates, impact of parameters like length of molecule, angle between different atoms, coupling situation of electrodes to molecule, the type of atoms used in a molecule's structure and other cases has made their development almost impossible. In this paper, there was an attempt to study previous works in order to, first, mention the effects of different conditions on circuit performance and, second, present an algorithm for designing gates so as to minimise the effects of these parameters on circuit performance.     

Au电极连接富勒烯C32分子的电子结构与传输特性

采用基于密度泛函理论(DFT)和非平衡格林函数(NEGF)的第一性原理方法对富勒烯C₃₂分子及在C₃₂分子的距离最远的两个碳原子处连接Au(1,1,1)电极的分子器件进行了电子结构和电子输运性质的研究.考虑到中间分子与Au电极间距离变化的情况,通过计算得出了在不同距离下分子器件的电子传输谱和I-V特性,分析了各器件的电子结构和电子输运特性产生的原因,并分析了电极与中间分子的连接距离及门电压对分子器件电子输运的影响.得出了电极与所连接的中间分子之     

Interaction of the uracil dipole-bound electron with noble gas atoms

Very diffuse, but localized, electrons trapped in dipole—bound states of polar polyatomic molecules may provide excellent targets for testing electron—molecule interactions. Ab initio calculations are used to investigate systems where a dipole—bound electron attached to a uracil molecule is interacting with noble gas atoms (He and Ne) and forming very weakly bound adducts. In these adducts, the noble gas atoms are separated from the uracil molecule by considerable distances, and the excess electron is suspended between the uracil molecule and the noble gas atom. Calculations are performed to determine the vertical electron detachment energies of these systems and to determine what happens when the excess electrons are removed from them.     

LCAO studies of hydrogen chemisorption on nickel: II. Cluster models for adsorption sites

The adsorption of single hydrogen atoms, investigated by means of cluster calculations, has been compared with the adsorption of hydrogen monolayers on periodic crystals (paper I). From the similarity of the adsorption energy curves we conclude that the (direct and indirect) interactions between adsorbed hydrogen atoms are relatively small up to monolayer coverage. For adsorption on different sites of ideal low index surfaces the stability decreases in the order Atop > Bridge > Centred. For Atop adsorption it increases with a decreasing number of nearest neighbours to the nickel atom in the NiH “surface molecule”, thus leading to especially strong adsorption sites at the edges of a stepped surface and to low stability in the notches. In general, we find that the Ni_nH “surface molecule” with n = 1, 2, 3 or 4 determines the equilibrium positions for H adsorption; the inclusion of one shell of neighbours to the nickel atoms is sufficient to explain the differences in adsorption energy. The Extended Hückel method is not well suited to study dissociative chemisorption of H₂, although some qualitative trends are correct.     

AlxOy(x=1—2,y=1—3)分子几何结构与稳定性的DFT研究

用密度泛函理论(DFT)的B31yp方法在6-311++g^水平上对Al_xO_y(x=1—2,y=2—3)分子的几何构型、电子结构、振动频率等性质进行了理论研究. 通过对基态结构的几何参数分析发现，它们的基态结构趋于直线或平面结构. 对基态结构的绝热电离能讨论表明，金属铝原子数一定时，氧原子数从1增加到3，其气态分子越来越稳定，铝原子数少的分子体系更稳定. 系统给出了该系列分子基态的几何参数、电子结构、光谱性质. Al₂O₃的C_2V三重态是该分子的能量最低结构. 关键词： xO_y分子')" href="#">Al_xO_y分子 密度泛函理论 结构与稳定性