Quenching of the fluorescence of solutions of complex molecules by nonradiative transfer of electronic-excitation energy to a saturable acceptor

The study puts toward a theoretical model describing the fluorescence parameters for concentrated solid solutions consisting of complex molecules of two types (donor-acceptor) with nonradiative transfer of electronic-excitation energy with intense pulse excitation. Consideration is given to the dynamics of quenching of the luminescence of the donor molecules due to transfer of electronic-excitation energy to the acceptor molecules. Numerical results are presented in the form of approximation formulas. To whom correspondence should be addressed. Belarusian State University, 4, F. Skorina Ave., Minsk, 220050, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 5, pp. 652–656, September–October, 1999.     

Estimation of photonic multipolar coupling ranges among quantum dots on the basis of time–energy uncertainty

We give a real use of the time–energy uncertainty principle for nanostructure circuit design consideration. The range of virtual as well as real photons mediating interactions among nanostructures is estimated as the product of the photon lifetime and its velocity, as in the meson exchange model for nucleon. This gives a new vista for near field interactions of electric nature in a solid, especially for the nonradiative internal energy transfer, which may be called the resonance dynamic multipole–multipole interaction (RDMMI). The length of the transition dipole is deduced from the 0.3 meV fine structure in our microphotoluminescence spectra of an individual coupled GaAs asymmetric quantum dots. Various multipoles and their potentials are estimated employing this dipole length. Then the ranges and lifetimes of the RDMMI are derived and plotted, together with the spatiotemporal consideration and the provisional structure of quantum circuits.     

Concentration self-quenching in solid solutions of complex organic molecules under intense excitation

A theoretical study was carried out to investigate concentration self-quenching which is nonlinear in intensity in a molecular system caused by nonradiative electronic excitation energy transfer to relatively long-lived acceptors that are formed in a solution and whose function is performed by molecules that have acquired the triplet state. It is shown that at ratios of constants of radiative and nonradiative transitions typical of complex molecules at concentrations of ∼10⁻³–10⁻² mole/liter substantial (2- to 10-fold) fluorescence takes place at intensities of excitation of ∼10⁴–10³ of the intensity of saturation for a singlet subsystem. Polarization characteristics of the system are analyzed. Belarusian State University, 4, F. Skorina Ave., 220050, Minsk, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 6, pp. 729–733, November–December, 1997.     

Probability estimate for intersystem crossings in naphthalene and acenaphthene in the presence of benzophenone

To a first approximation in perturbation theory, we have obtained expressions for the rate constants for intersystem crossings in acceptor molecules. We show that exchange interactions between the components of the donor-acceptor pair can change the probability of intersystem crossings for both radiative T → S₀ and nonradiative S₁ → T transitions. The theoretical conclusions are supported by the results of experimental studies. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 4, pp. 550–553, July–August, 2006.     

Kinetics of nonequilibrium processes excited in broad-band dielectrics by synchrotron radiation

Luminescence spectroscopy with subnanosecond time resolution is used to study features of nonequilibrium processes excited in several broad-zone dielectrics (mainly inorganic scintillators) by pulses of synchrotron radiation (SR). When excitation density exceeds a certain level, which is different for each material, there is an abrupt change in the kinetics of relaxation of the nonequilibrium states. This change is accompanied by nonuniform broadening or shortwave shifting of the luminescence spectrum and a drop in quantum light yield. The decay time for natural luminescence decreases by 1–3 orders, to nanoseconds, and is independent of temperature within the range 80–450 K. The build-up stage disappears in the kinetics of luminescence of Ce³⁺-centers and decay time is reduced by a factor of 2–4. Density effects are found to be independent of the conditions under which the material is exposed to SR. A model is proposed in which density effects are related to nonradiative energy transfer from the upper excited states of the luminescence centers to external quenching centers. The contribution of the space charge induced by SR is also examined. Ural State Technical University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 120–135, November, 1996.     

Effect of the polymethine chain length, the polarity and temperature of the medium on the spectroscopic properties of merocyanine dyes

We have studied the luminescent spectral properties and calculated the quadratic polarizability of dimethine, tetramethine, and hexamethine merocyanines based on 1,3-dihydro-1,3,3-trimethyl-(2H)-indol-2-ylidene and malonodinitrile in solutions and polymer films at room temperature and 77 K. We have shown that increasing the polarity of the solvent and lengthening the polymethine chain in the studied merocyanines lead to an increase in fluorescence quantum yields and narrowing of the fluorescence bands. This is explained by the decrease in bond length alternation and weakening of vibronic interactions in the singlet-excited fluorescent state. The mirror symmetry in the structured absorption and fluorescence spectra of merocyanine dyes in ethanol at 77 K, observed here for the first time, is due to enhancement of electrostatic interactions of the merocyanine and solvent molecules. Increased stiffness of the medium considerably decreases the probability of nonradiative processes, and the major channel for deactivation of the electronic excitation energy at 77 K is fluorescence. The higher values of the quadratic polarizability (6.0·10⁻²⁸ esu in ethanol and 3.3·10⁻²⁸ esu in chloroform) for hexamethine merocyanine, estimated by the solvatochromic method, lets us consider this compound as a promising material for designing nonlinear optical converters for harmonics of laser radiation. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 1, pp. 26–35, January–February, 2006.     

Nonradiative energy transfer in carbocyanine dye compositions inside surfactant micelles

Utilizing forced concentration of carbocyanine dye molecules DiI and DiD within a surfactant micelle, we have detected nonradiative transfer of electronic excitation energy for low initial dye concentrations in the aqueous micellar solution. Luminescence and fluorescence anisotropy decay studies allowed us to establish that in the micelles, the hydrophilic head of the dye is in contact with the water while the C18H37 groups are located in the hydrocarbon core of the micelle. We show that due to the structural features of the DiD acceptor molecule, rotational diffusion of the acceptor in the micelle is more free than for the donor DiI, the motion of which is constrained in the micelle. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 2, pp. 152–157, March–April, 2006.     

Signs of structural changes in molecules in IR spectra with pulsed heating

We have shown that in slow thermal reactions of complex molecules, effects of nonradiative transitions due to quantum beats between resonant states of the combining molecular structures can be observed in conventional (without high time resolution) IR absorption spectra, as oscillations in the intensities of individual lines. We suggest a method to ensure the required level of coherence for the oscillations in an ensemble of molecules, based on application of pulsed heating to the molecular system. Detection of the qualitatively new effects by traditional IR spectroscopy methods, including their quantitative characteristics, considerably increases the information content of the spectral data obtained and makes it possible to use such highly developed experimental methods to study chemical reactions, including the reaction dynamics. The range of these reactions is quite broad, encompassing both “laboratory” and “natural” (geochemistry, ecology, etc.) processes with characteristic times on the order of minutes or more. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 6, pp. 738–743, November–December, 2007.     

The effect of fluctuations of a classical exterior medium on tunneling nonradiative processes in molecules

We examine nonradiative transitions in molecules with allowance for the effect of a classical polar exterior medium on tunneling charge transport. The approach allows for the vibrational frequencies of a molecule in the electron transition. In the case of slow fluctuations, the theory predicts a low-temperature (non-Arrhenius) increase in the tunneling nonradiative transition rate, and the results agree qualitatively with the experimental data. When the fluctuations of the exterior medium are rapid, at certain values of the molecular parameters the tunneling decay rate is found to decrease with increasing temperature because the conditions needed for resonant tunneling are violated. Zh. éksp. Teor. Fiz. 114, 1944–1953 (December 1998)     

Conformal transitions of the laurdan molecule in the absorption and fluorescence spectra

The fluorescent probe molecule – laurdan (6-dodekanoil-2-dimetilamin naphthalene) – is investigated by experimental and quantum-chemical methods. The influence of the structure non-rigidity on the dipole moments, arrangement of energy levels, and distribution of charges in the laurdan molecule is studied. An optimized structure is obtained and analyzed by the molecular dynamics method. Several structures with different rotation angles of the dimethylamino group are investigated, for which energy, oscillator forces, and nature of electron states are calculated. Fluorescence spectra of the laurdan molecule in an inert solvent are interpreted. Centers of possible interaction of the molecule with a proton-donor solvent are established. Rate constants of radiative and nonradiative processes and quantum fluorescence yields of the examined probe are calculated.     

Spectral fluorescence and polarization characteristics of <Emphasis Type="Italic">Z,Z</Emphasis>-bilirubin IXα

We have studied the spectral fluorescence and polarization characteristics of Z,Z-bilirubin IXα, at room temperature in chloroform and in aqueous buffer medium, within an equilibrium complex with human serum albumin (HSA), and also under low temperature conditions (T = −100°C) in isobutyl alcohol. We have observed a bathochromic shift of the fluorescence spectra, which is most pronounced for the bilirubin-albumin complex. The following are considered as possible reasons for the observed dependence of the position of the fluorescence (fluorescence excitation) spectra on the excitation (detection) wavelength: structural and spectral differences between the chromophores making up the bilirubin molecule; conformational heterogeneity of the pigment in solution; a contribution to the fluorescence from molecules which have not completed the vibrational relaxation process; inhomogeneous orientational broadening of the levels; heterogeneity of the microenvironment of the chromophores in the protein matrix. We show that polarized fluorescence of bilirubin occurs at room temperature, due to the anomalously short fluorescence lifetime τ (picosecond or subpicosecond ranges). Despite such a short τ, the absorption and emission polarization spectra suggest the presence of intramolecular nonradiative singlet-singlet energy transfer when bilirubin is excited to high vibrational sublevels of the S₁ state (degree of polarization p = 0.11–0.12). When fluorescence is excited on the long-wavelength slope of the absorption band, no transfer occurs: the degree of polarization (p = 0.46−0.47) is close to the limiting value (p = 0.50). We discuss the question of the role played by exciton interactions between chromophores in the bilirubin molecule when it is excited. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 1, pp. 108–119, January–February, 2007.     

On transverse momentum event–by–event fluctuations in string hadronic models

Transverse momentum event–by–event fluctuations are studied within the string–hadronic model of high energy nuclear collisions, LUCIAE. Data on non–statistical fluctuations in p+p interactions are reproduced. Fluctuations of similar magnitude are predicted for nucleus–nucleus collisions, in contradiction to the preliminary NA49 results. The introduction of a string clustering mechanism (Firecracker Model) leads to a further, significant increase of fluctuations for nucleus–nucleus collisions. Secondary hadronic interactions, as implemented in LUCIAE, cause only a small reduction of fluctuations. Received: 23 October 1998 / Published online: 11 March 1999     

Theoretical models for interisomer transitions of complex molecules and their spectral manifestations

We have used computer simulation to compare theoretical models for describing interisomer transitions of complex molecules and their spectral manifestations. We have shown that the kinetics of the intramolecular processes and time-resolved spectra, taking into account quantum beats between resonant (bound) states of the isomers (or isolated level subsystems for one isomer form), can be described not only by using a general molecular model in which the resonant levels of the subsystems act as a single level of a mixed state, with a time-dependent wave function in the form of quantum beats, but also by using a model interpreting the beat effect as a nonradiative transition. These models are completely equivalent: the parameters describing them have the same values, and numerical differences in the results obtained are no greater than 1% and are due to numerical round-off errors in the calculations and not differences between the models. The second model is preferred because it is graphically clear and conventionally used for describing and interpreting intramolecular processes, but it does take somewhat longer (∼10%) to run the simulation. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 1, pp. 36–41, January–February, 2006.     

Temperature and injection current dependent electroluminescence study of GaInP/AlGaInP quantum well laser diode grown using tertiarybutylarsine and tertiarybutylphosphine

GaInP/AlGaInP triple quantum well (TQW) lasers, grown by metalorganic chemical vapor deposition (MOCVD) using tertiarybutylarsine (TBAs) and tertiarybutylphosphine (TBP), were fabricated with a pulsed anodic oxidation (PAO) process. The devices worked at room temperature (RT) with the lowest threshold current density (J_th) of 1.5 kA/cm² ever reported for GaInP/AlGaInP lasers grown using TBAs and TBP. Temperature dependent (35–250 K) electroluminescence (EL) study of the GaInP/AlGaInP laser diode showed almost the same luminescence quenching behavior at a high temperature region (120–250 K), independent of the injection current (100–150 mA). A model involving a nonradiative recombination mechanism was presented to interpret the EL quenching behavior over the experimental temperature range. The nonradiative recombination centers in the Al-containing barrier or cladding layer are believed to contribute to the loss of carriers via nonradiative recombination. PACS 78.60.Fi; 71.20.Nr; 78.67.De; 81.15.Gh; 42.55.Px     

Enhancement of fluorescence of porous silicon upon saturation by liquid crystal

The fluorescence of samples of porous silicon of various morphologies that are filled with a liquid crystal (LC), n-pentyl-n′-cyanobiphenyl (5CB), is studied. The fluorescence spectra of the sample, along with the long-wavelength band of porous silicon with a maximum in the range 627–667 nm, exhibit a short-wavelength band of 5CB with a maximum in the range 385–410 nm. The radiative relaxation times of porous silicon and 5CB lie in the micro- and nanosecond ranges, respectively. It is found that the filling of pores with 5CB enhances the fluorescence of porous silicon by two to three times. This enhancement is caused by non-radiative energy transfer from 5CB to the porous matrix as a result of efficient interactions between LC molecules and pore walls. Using IR spectroscopy, it is shown that the formation of hydrogen bonds between cyano groups of 5CB molecules and silanol groups of pore surface is the predominant type of these interactions. A transfer mechanism is suggested according to which excited associates of 5CB molecules transfer their energy via surface channels to excitons of porous silicon, enhancing its fluorescence.     

Relating multihadron production in hadronic and nuclear collisions

The energy-dependence of charged particle mean multiplicity and pseudorapidity density at midrapidity measured in nucleus–nucleus and (anti)proton–proton collisions are studied in the entire available energy range. The study is performed using a model, which considers the multiparticle production process according to the dissipating energy of the participants and their types, namely a combination of the constituent quark picture together with Landau relativistic hydrodynamics. The model reveals interrelations between the variables under study measured in nucleus–nucleus and nucleon–nucleon collisions. Measurements in nuclear reactions are shown to be well reproduced by the measurements in pp/[`(p)]p{\bar{\mathrm{p}}}{\mathrm{p}} interactions and the corresponding fits are presented. Different observations in other types of collisions are discussed in the framework of the proposed model. Predictions are made for measurements at the forthcoming LHC energies.     

Rate constants of nonradiative intersystem crossing transition S1(ππ*) ? T1(ππ*) in molecules of aromatic compounds with heteroatoms

In terms of the adiabatic theory of interactions, we consider the results of the theoretical estimation of the rate constants K _ST of the nonradiative intersystem crossing conversion S ₁(ππ*) ⇝ T ₁ ^S (ππ*) for nine aromatic molecules containing 10–14 carbon atoms and one or two heavy (many-electron) oxygen or chlorine atoms.     

Soft diffraction at the LHC: a partonic interpretation

We present a ‘new generation’ model for high energy proton–proton ‘soft’ interactions. It allows for a full set of multipomeron vertices as well as for including multichannel eikonal scattering. It describes the behaviour of the proton–proton total, σ_tot, and elastic, dσ_el/dt, cross sections together with those for low- and high-mass proton dissociation. Although the model contains a comprehensive set of multipomeron diagrams, it has a simple partonic interpretation. Including the more complicated multipomeron vertices reduces the absorptive effects as compared to the predictions in which only the triple-pomeron vertex is considered. Tuning the model to describe the available ‘soft’ data in the CERN ISR–tevatron energy range, we predict the total, elastic, single- and double-diffractive dissociation cross sections at the LHC energy. An inescapable consequence of including multichannel eikonal and multipomeron effects is that the total cross section is expected to be lower than before: indeed, we find σ_tot≃ 90 mb at the LHC energy. We also present differential forms of the cross sections. In addition, we calculate soft diffractive central production.     

The Effect of N-methylation on Photophysical Properties of 3-Aminoquinoline

It has been reported previously that the photophysics of 3-aminoquinoline (3AQ) is governed by a flip–flop motion of its amino group in apolar solvents and intersystem crossing in polar solvents. The nonradiative rates are governed by more than one solvent parameters, like polarity and hydrogen bonding ability of the solvent. So, 3AQ is not a well-behaved probe of any individual solvent parameter. In the present work, 3AQ has been modified synthetically; replacing an amino hydrogen atom with a methyl group and photophysical properties were studied in 22 different apolar, polar-aprotic and polar-protic solvents. It is found that Stokes’ shifts and fluorescence quantum yields exceptionally low in apolar solvents as compared to those in other solvents. Such substitution causes a decrease in the extent of the effect of the hydrogen bonding ability of the solvent and that nonradiative rate become a more regular function of polarity. However, the flip–flop appears to continue to be the major nonradiative pathway, as the nonradiative rates decrease with increase in micropolarity.     

Electron excitation energy transfer in Me7Eu2UO2(PO4)5 (Me — Na, Rb, Cs) crystals

The article considers the luminescence-kinetics properties of crystals of ternary uranyl orthephosphates Me₇Eu₂UO₂(PO₄)₅ (Me — Na, Rb, Cs) obtained by the methods of solid-phase synthesis. The main parameters of conversion of the electron excitation energy in the donor-acceptor UO ₂ ²⁺ —Ln³⁺ system are determined. The competition between the processes of nonradiative dissipation and energy transfer from UO ₂ ²⁺ to Eu³⁺ has been revealed. It is shown that the rate of the processes of nonradiative transitions in the uranyl complex is determined by the degree of distortion of its local field, while the luminescence lifetime of the acceptors depends on the energy of electrostatic interaction between Eu³⁺ and oxygen atoms of its first coordination sphere. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 3, pp. 333–335, May–June, 2000.