Homo- and Heteroannihilation of Triplet-Excited Bengali Rose and Anthracene Molecules on Silica in a Wide Temperature Range

The processes of triplet-triplet annihilation of the triplet-energy donor of Bengali rose dye and anthracene acceptor adsorbed on the surface of wide-pore silica have been investigated in the temperature range 150–290 K. The rate constants of homo- and heteroannihilation of the molecules of luminophors have been determined in a wide temperature range. It has been established that the processes of energy transfer in the initial (after photoexcitation) periods of phosphorescence decay are described by the Inokuti–Hirayama equations modified in the present work for a two-dimensional problem, whereas in the mean-time and long-time periods the kinetics of phosphorescence decay becomes similar to the fractal one.     

Inductive-resonant triplet-triplet annihilation in solid solutions of erythrosine

Experimental investigations of annihilation-induced delayed fluorescence and phosphorescence of frozen ethylene glycol solutions activated by erythrosine were carried out. It is found that the kinetics of the annihilation-induced delayed fluorescence is nonexponential in the initial stage, and approaches an exponential decay at later stages with the lifetime equal to half the triplet-state lifetime. It is shown that experimental data agree well with the theory proposed to describe triplet-triplet annihilation by an inductive-resonant mechanism in solid solutions of complex organic molecules. Belarusian State University, 4, F. Skorina Ave., Minsk, 2200050, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 5, pp. 629–632, September–October, 1997.     

Heterogeneous triplet-triplet annihilation of erythrosine and anthracene molecules on a fractal anodized aluminum surface

We have studied exchange resonance processes of homogeneous triplet-triplet annihilation and heterogeneous triplet-triplet annihilation for erythrosine and anthracene molecules on an anodized aluminum surface over a broad temperature range. We have shown that the kinetics of the considered processes are determined by the dimensionality of the molecular clusters on the porous anodized aluminum surface. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 2, pp. 205–210, March–April, 2007.     

Kinetics of triplet-triplet absorption of anionic water-soluble porphyrins

It was established that in aqueous solutions of anionic porphyrins the processes of triplet-triplet (T-T) annihilation are absent (K₂<2.5·10⁵ M⁻¹ sec⁻¹), while a delayed annihilation fluorescence can be detected for these porphyrins in methanol (K₂≊3.5·10⁷ M⁻¹ sec⁻¹) and for their lipophilic analogs in organic solutions (K ₂≊2.5·10⁹ M⁻¹ sec⁻¹), and the kinetics of absorption of the latter porphyrins in triplet states is dependent on the intensity of the exciting radiation. The extremely small constant of T-T annihilation of anionic porphyrins can be due to the formation of a relatively dense solvate shell consisting of water molecules around the charged groups of the porphyrin molecules, which increases steric barriers and thus prevents an exchange-resonance transfer of energy between triplet excited molecules in aqueous solutions. It is also shown that porphyrin molecules can electrostatically repel one another when in their structure there are charged groups. To whom correspondence should be addressed. Deceased. Institute of Molecular and Atomic Physics, National Academy of Sciences of Belarus, 70 F. Skorina Ave., Minsk, 220072, Belarus; e-mail: llum@imaph.bas-net.by. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 6, pp. 791–795, November–December, 1999.     

Triplet-triplet transfer of electronic energy upon nonequilibrium vibrational excitation of triplet molecules

The specific features of the triplet-triplet (T-T) transfer of electronic excitation energy in a gas phase upon nonequilibrium vibrational excitation of the triplet molecules of a donor were studied for an anthraquinone-diacetyl donor-acceptor pair using the time-resolved slow fluoresence of anthraquinone and sensitized phosphorescence of diacetyl. It is shown that in the gas phase, which allows regular control of the number of collisions, competition between the processes of T-T transfer and intermolecular vibrational relaxation is observed for nanosecond time resolution. The T-T transfer rate for the molecular system investigated exceeded the rate of intermolecular vibrational relaxation k_V in the triplet state T₁ of the donor. The effectiveness of the T-T transfer of energy by vibrationally excited molecules turned out to be higher than the effectiveness of transfer by thermalized ones, but even the highest of them was much less than unity. An increase in the equilibrium temperature of vapors led to a decrease in the effectiveness of transfer for both vibrationally excited and thermalized triplet molecules, thus indicating the importance of the collisional complex in the intermolecular process studied. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 4, pp. 474–479, July–August, 2000.     

Delayed Luminescence of 8-Aza-D-Homogone-1,3,5(10),13-Tetraene-12,17a-Dione in the Gas Phase and Solid Solutions

It is shown that the delayed-luminescence spectrum of 8-aza-D-homogone-1,3,5(10),13-tetraene-12,17a-dione (8-aza-D-homogonane) in the gas phase comprises a band of thermally activated delayed fluorescence and a band of annihilation delayed fluorescence that are respectively due to the C- and D-centers representing products of photo-and thermotransformations of the initial steroid for which we failed to detect delayed luminescence. The triplet-triplet energy transfer from the C-centers to the D-centers has been detected and its efficiency has been determined. It has been established that, in a frozen hexane solution (T = 77 K) of the substance taken from a vacuum cuvette after the investigation of initial 8-aza-D-homogonane in the gas phase, only the C- and D-centers phosphoresce. For a frozen solution of the initial steroid in a vitrifying mixture of tetrahydrofuran and toluene, a phosphorescence of both the steroid itself (λ _max ^phos = 415 nm) and the C- and D-centers (λ _max ^phos = 498 and 532 nm, respectively) was detected. This indicates that even the initial steroid kept at room temperature contains products of its transformation whose concentration increases on irradiation and heating. The C- and D-centers are stable molecules.__________Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 2, pp. 192–197, March–April, 2005.     

Spectral characteristics of luminescence of solutions of complex molecules under conditions of electronic excitation transfer to a saturable acceptor in the case of inhomogeneous broadening of electronic energy levels

Spectral characteristics of solutions of complex molecules under conditions of inhomogeneous broadening of energy levels are considered in the case when the nonlinear dependence of the population of molecular states on the excitation intensity is determined not by saturation of molecular levels but by exchange of the electronic excitation energy with the environment. Calculations have shown that the dependence of the position of the fluorescence spectrum on the excitation frequency is nonmonotonic in solutions of the type and varies substantially with the excitation intensity. Belarusian State University, 4, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 2, pp. 164–168, March–April, 1997.     

Energy yield of fluorescence of complex organic compounds upon electron excitation

With use of electron energy loss spectra for vapors of anthracene, perylene, 1,4[di(2,5-phenyloxazolyl)] benzene, and paratherphenyl the energy yields of fluorescence are calculated for electron collision. It is shown that they are considerably smaller than those for optical excitation conditions. Deceased Institute of Molecular and Atomic Physics of the National Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 1, pp. 146–148, January–February, 1998.     

Regularities of triplet-triplet annihilation of aromatic hydrocarbons in aqueous micellar solutions of sodium dodecyl sulfate

Investigation of deactivation processes in triplet states of a series of aromatic hydrocarbon molecules (antracene, 1,2-benzantracene, and 3,4-benzpyrene) made it possible to reveal the presence of triplet-triplet annihilation of the molecules in aqueous micellar solutions of sodium dodecyl sulfate. It is shown that the effect of microheterogeneous solutions on the process of triplet-triplet annihilation manifests itself in an increase in the probability of excimerization upon dissociation of triplet pairs of 1,2-benzantracene and 3,4-benpyrene molecules compared to one-component solutions. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 5, pp. 626–628, September–October, 1997.     

Heteroannihilation of the excited states of associates and monomers of fluorescein dyes on the silica surface at low temperatures

The processes of homo-and hetero-triplet—triplet annihilation (TTA) of Bengali rose on the spongy silicon surface have been investigated. It has been found that upon pulse photoexcitation on the silica surface photophysical processes involving the triplet states of monomers and their associates can develop. It has been shown that the processes of hetero-TTA are inhibited due to the decomposition of associates under the influence of hexane molecules in the molecular clusters of the dye adsorbates. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 6, pp. 734–737, November–December, 2005.     

Characteristic features of carbazole phosphorescence quenching by benzophenone molecules in toluene at 77 K

We have studied the characteristic features of carbazole phosphorescence quenching by benzophenone in toluene at 77 K. We have shown that the decrease in the relative phosphorescence intensity for carbazole (energy donor) by a greater factor than we see for the relative change in its decay time is due to the fact that a change in the phosphorescence decay time occurs only for carbazole molecules participating in triplet-triplet energy transfer, while the substantial decrease in the phosphorescence intensity for carbazole with no change in the phosphorescence decay time is connected with quenching of its singlet states. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 4, pp. 554–556, July–August, 2006.     

Effect of Temperature on the Rate of Triplet–Triplet Annihilation of 1,2-Benzanthracene in a Polymer Matrix

The process of triplet–triplet annihilation (TTA) of 1,2-benzanthracene (1,2-BA) incorporated into polymer films of polyvinyl butyral has been investigated in the temperature interval 80–360 K. An analysis of the kinetics of the decay of delayed annihilation fluorescence (DAF) of 1,2-BA has shown that the process of the triplet excitation energy transfer in a disperse medium of the polymer at distant times of the DAF decay can be described using the approximation of random walks of the triplet energy in the inhomogeneous medium of the polymer. At low temperatures, at the initial times of DAF decay the TTA process is described with the aid of a model of static annihilation.     

Intermolecular Vibrational Relaxation in Mixtures of Excited Benzophenone and Anthraquinone Molecules with Water Vapor

The intermolecular vibrational energy transfer from triplet molecules of benzophenone and anthraquinone to H₂O molecules has been investigated. To determine the rates of establishment of vibrational (V-V) and thermal (V-T) equilibrium in a vibrational quasi-continuum of mixed singlet-triplet levels, the dependences of the decay rates and intensities of the fast and slow components of delayed fluorescence on the H₂O vapor pressure have been investigated. For V-V relaxation, the efficiencies ₁ and the mean energies E transferred per collision in mixtures with H₂O and other polyatomic foreign gases have been compared. It has been established that the efficiencies ₁ for quasi-resonant vibrational energy transfer (V-V) from benzophenone and anthraquinone to H₂O are an order of magnitude lower than the gas-kinetic ones and lower than those obtained under the same experimental conditions for such foreign gases as C₅H₁₂, SF₆, and CCl₄, and decrease with increasing temperature in the 433–513 K range. It has been concluded that the mechanism of V-V relaxation in mixtures with H₂O are determined by long-range attractive forces. In mixtures with H₂O, no acceleration of V-T relaxation due to the formation of hydrogen bonds has been revealed. The low-efficiency thermalization process (V-T relaxation) is controlled by short-range repulsive forces, and the differences between the intensities ₂ for mixtures of benzophenone and anthraquinone with H₂O and other polyatomic gases are determined by the change in the reduced mass of interacting molecules.     

White luminescence of a system based on poly(9,9-di(ethylhexyl)fluorene) activated by fluorescent dyes

Luminescence has been studied for poly(9,9-di(ethylhexyl)fluorene) containing laser dyes which fluoresce in the green and red spectral regions. It has been shown that white luminescence can be obtained as a result of singlet-singlet energy transfer from the polymer matrix to the dyes at certain concentrations of the latter. Two systems are proposed that make it possible to obtain equi-energy white emission and white emission, taking into account the characteristics of the spectral sensitivity of the human eye. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 1, pp. 37–41, January–February, 2007.     

Influence of Vibrational Excitation of Triplet Molecules of Anthraquinone on the Photochemical Processes in Gas Mixtures with Amines

By the quenching of the delayed fluorescence (DF) of anthraquinone vapors by aliphatic amines (diethylamine, dibutylamine, cyclohexylamine) and pyridine the photoinduced processes proceeding with the participation of vibrationally excited triplet molecules of anthraquinone have been investigated. The DF quenchingrate constants K _q varying from 1·10⁶ sec^–1·torr^–1 in mixtures with diethylamine to 7·10³ sec^–1·torr^–1 in mixtures with pyridine have been estimated. A correlation between the values of K _q and the ionization potentials of foreign gases confirming the important role of interactions with charge transfer in the quenching of triplet molecules in the gas phase has been established. The influence of other relaxation processes on the DF quenching is considered. It is shown that the intermolecular vibrational relaxation in the T ₁ triplet state leading to the establishment of relaxation equilibrium at a vibrational temperature T _vib considerably increasing the medium temperature is the fastest process among the biomolecular processes (rate constants K _col ^V > 10⁶ sec^–1·torr^–1 > K _q). The values of T _vib and the vibrational energies E _vib of the triplet molecules after the energy exchange in the collisional complex have been estimated. It has been concluded that the photochemical reaction yield is determined by the intermolecular processes proceeding in the T ₁ state at a vibrational equilibrium characterized by high values of T _vib. The influence of E _vib of triplet molecules on the DF quenching rates at a photoinduced electron transfer is considered.     

Dynamic and stationary characteristics of nonlinear luminescence in molecular layers with electronic-excitation energy transfer

We carry out an analysis of the characteristics of nonlinear luminescence of a multicomponent layer system consisting of layers of molecules of a sensitizer, donor, and acceptor with inductive-resonance transfer of energy between the components of the molecular ensemble. We show that in a stationary regime bistable dependences of the populations of excited states of molecules on excitation intensity are realized without external feedback. For pulse pumping, we show the possibility for forming response-luminescence pulses with widely variable characteristics: shape, duration, intensity, and delay. Belorussian State University, 4, F. Skorina Ave., Minsk, 220050, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 2, pp. 190–196, March–April, 1999.     

Quenching of fluorescence of conjugated poly(p-phenylene) polymers by benzil and dimethylaminobenzil molecules

We have studied the mechanisms for quenching of the fluorescence of conjugated poly(p-phenylene) polymers by benzil and dimethylaminobenzil molecules. We have shown that molecules in the diketone series are quenching agents for the fluorescence of the indicated polymers, and can serve as singlet-triplet converters capable of populating the triplet state of the polymer. We have observed that the efficiency of quenching of the fluorescence of the studied polymers depends considerably on the presence of bulky side groups in the polymer or in the activator molecules. Based on analysis of the data obtained, we conclude that in the case of a rigid planar structure for the polymer, a significant contribution to quenching of its fluorescence comes from not only singlet-singlet energy transfer but also charge transfer, leading to formation of intermolecular complexes (exciplexes). __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 6, pp. 756–762, November–December, 2006.     

Energy transfer relation of a novel Ce~(3+)/Pr~(3+)/Eu~(3+) co-doped Sr_(2.975-x)La_xAlO_(4+x)F_(1-x) solid solution phosphor

The photoluminescence properties and energy transfer of a new Ce3+/ Pr3+/ Eu3+co-doped solid-solution composition of Sr2.975-xLaxAlO4+xF1-x(LSAF) phosphor are investigated. Upon doping Pr3+into lattices of LSAF:Ce host,a shoulder emission peak is observed at about 620 nm, owing to the transition of1D2→3H4. Addition of Eu3+to LSAF:Ce3+, Pr3+phosphor results in a sharp emission peaked at 675 nm for the5D0→7F3transition and an increase of the intensity of red emission for Pr3+with increasing Eu3+concentration. The pathways of energy transfer among Ce3+, Pr3+, and Eu3+are proposed to be responsible for color addition of a red component to the primary yellow emission,enabling a potential adjustable color for blue excitable warm white.     

Cluster model for complex compounds of hexavalent uranium

We have studied the regular patterns of the change in the electronic transition frequency in low-temperature luminescence spectra of uranyl trinitrate and tetranitrate crystals with alkali metal cations or an NH ₄ ⁺ group as the outer-sphere cations, as a function of the ionization potential of the latter. An analogous study was carried out as a function of the ratio of the concentrations of impurity and matrix for different cations in mixed crystals and solid solutions. Analysis of the results obtained, together with available crystallographic data, allowed us to propose a cluster model for the uranyl complex. The observed regular patterns are also explained from the standpoint of statistical thermodynamics. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 5, pp. 588–591, September–October, 2006.