Kinetics of the Decay of Prolonged Luminescence of Disordered Chrysene under the Conditions of Nonequilibrium Transfer of Energy

We present the results obtained in investigation of the decay of the prolonged luminescence of disordered chrysene in a microsecond range. At the temperature of liquid nitrogen, a highly nonexponential decay of both phosphorescence and annihilation of delayed fluorescence is observed. The observed character of decay is due to relaxation of the energy of electronic excitation in a system of energydisordered centers, when the value of kT is much smaller than the width of the excitedstate energy distribution. At the same time, in the system investigated there is a classical relationship between phosphorescence and delayed fluorescence, i.e., the rate coefficient for the reaction of triplettriplet annihilation is a constant.     

Kinetics of Triplet-Triplet Annihilation in Organic Glasses

In the present paper, the results of the investigation of the decay kinetics of delayed luminescence of organic glasses are presented. A strong deviation of the decay of both phosphorescence and annihilation delayed fluorescence from the exponential law is observed. This effect is shown to be due to the relaxation process of electronic excitation energy in the system with large energetic disorder. At the same time, the presence of two time intervals in which the rate coefficient for triplet-triplet annihilation (TTA) reaction shows different dependence on time is observed. On a short time scale the classical behavior is observed, i.e., the reaction is well described by the second-order equation with a time-independent rate coefficient. At the limit of long times, we have strong dependence of rate coefficient on time, i.e., the electronic excitation energy transport is dispersive. It is shown that behavior observed for the rate coefficient for TTA reaction is due to the relaxation process (on short time scale) and the equilibrium energy migration (in long time limit).     

Kinetics of long-lived luminescence of eosin in Langmuir-Blodgett films

The spectral and kinetic properties of photoluminescence of mixed Langmuir-Blodgett (LB) films of eosin decyl ether and palmitic acid on a solid substrate are studied. The electronic absorption and fluorescence spectra of the films are identical to the spectra of the dye in ethanol. An increase in the dye concentration in a monolayer results in the appearance of a dimer absorption band, quenching of fluorescence of monomers, and the red shift of the spectral bands. At 90 K, the distinct phosphorescence and delayed fluorescence bands of LB films were observed. The decay kinetics of phosphorescence and delayed fluorescence is nonexponential. It is shown that the decay curve of delayed fluorescence is determined by triplet-triplet annihilation (TTA) and T ₁→S₁ triplet-singlet intersystem crossing (IS). The initial nonexponential phosphorescence decay is caused the dominant contribution of TTA to the decay of triplet molecules. The experimental data are interpreted based on the mechanisms of exchange-resonance and inductive-resonance annihilation.     

Phosphorescence of pi-conjugated oligomers and polymers

We observed phosphorescence from a ladder-type poly-(para-phenylene) and an analogous oligomer containing five phenylene rings. The spectra are similar to the intrinsic fluorescence spectra and bear out a singlet-triplet splitting of 5000 cm(-1) (polymer) and 6800 cm(-1) (oligomer). Phosphorescence decay of the polymer occurs on a 10-100-micros scale obeying a power law and suggestive of nonradiative quenching, while that of the oligomer is asymptotically exponential with an intrinsic decay time of approximately 250 ms. The polymer also exhibits delayed fluorescence. It originates from delayed recombination of geminate electron-hole pairs rather than from triplet-triplet annihilation.     

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.     

Features of sensitized phosphorescence and delayed annihilation fluorescence spectra of coronene in frozen solutions

We have studied the sensitized phosphorescence spectra of coronene in toluene and its delayed annihilation fluorescence spectra in n-decane at 77 K. We show that as a result of perturbation of electronic states by exchange interactions, intensity redistribution occurs in both the sensitized phosphorescence spectrum and the delayed annihilation fluorescence spectrum. The nonzero probability of the symmetry-forbidden radiative 0–0 transition is explained by the lower symmetry of the bimolecular system compared with the symmetry of the coronene molecule.     

Recombination Prolonged Luminescence of Indole and Tryptophan in a Solution at Room Temperature

Prolonged luminescence of tryptophan and indole in liquid solutions of different polarity has been registered in a microsecond time-scale at room temperature; by nature it differs from phosphorescence or delayed fluorescence of P and E types. The data presented suggest that the observed prolonged luminescence is caused by recombination of the radicals formed upon UV irradiation of indole chromophores by laser pulses.     

Kinetics of annihilation of triplet excitationsand decay of delayed fluorescence for isolated 1,12-benzoperylene pairs

We studied the annihilation kinetics for triplet excitations in isolated pairs of organic molecules and their delayed fluorescence decay using a new mathematical model for the process. According to this model, the intensity of delayed annihilation fluorescence (DAF) for isolated pairs is directly proportional to the number of pairs in which both molecules are found in the excited triplet state. We show that the decrease in such pairs and the decay of their delayed annihilation fluorescence occur according to an exponential law in the absence of random scatter in the deactivation rate constants for the triplet excitations. The results of an experimental study of the DAF decay kinetics for 1,12-benzoperylene in n-hexane at 77 K, where triplet–triplet annihilation occurs in isolated pairs, confirm the validity of the theoretical conclusions.     

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.     

Delayed fluorescence and phosphorescence of tris-(8-hydroxyquinoline)aluminum (Alq3) and their temperature dependence

This paper reports on delayed luminescence measurements of tris-(8-hydroxyquinoline)aluminum (Alq₃) after optical excitation; these identify two bands in the emission spectrum: delayed fluorescence and phosphorescence. This is shown for different crystalline phases and for evaporated films. The assignment of the low-energy band to the phosphorescence is confirmed by lifetime measurements, and triplet energies of the meridional isomer in the -phase and the facial isomer in the δ-phase are determined from the well-resolved vibronic progressions of the phosphorescence as 2.11±0.1 and 2.16±0.1 eV, respectively. Lifetimes of the delayed fluorescence and the phosphorescence are determined for a temperature range from 6 to 150 K, and we measured the temperature dependence of the delayed photoluminescence spectra.     

On the temperature dependence of the phosphorescence of CaF2 : Mn phosphor in different atmospheres

The temperature dependence inthe region of 24–150°C of the phosphorescence of CaF₂ : Mn phosphor in the atmospheres of nitrogen gas, vacuum and moisture-saturated air were studied. A decay formula was found to adequately describe the rate of decay of the trapped electrons — which is assumed to be proportional to the amount of phosphorescence observed — in thermal traps. In nitrogen gas and vacuum the decay constants of the trapped electrons are dependent only on the storage temperature and not on the storage atmosphere of the phosphor. A slight effect of water on the rate of decay of the trapped electrons was also observed.     

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.     

Size effects in triplet-triplet annihilation: I. Standard and statistical approaches

The dynamics of triplet-triplet annihilation is theoretically studied in linear chains and nanoparticles as a function of size M, the rate of excitation migration W, and the rate of excitation annihilation V. It is shown that a sum of two exponentials is usually sufficient for fitting experimental phosphorescence and triplet-triplet absorption decays. The first term describes the decay of domains containing initially one triplet, while the second term reflects the disappearance of domains containing initially two triplets.     

Photochemical reactions of triplet benzophenone and anthraquinone molecules with amines in the gas phase

The intermolecular photoinduced reactions between triplet ketone molecules and aliphatic amines and pyridine are studied by the quenching of delayed fluorescence of anthraquinone and benzophenone vapors by diethylamine, dibutylamine, cyclohexylamine, triethylamine, and pyridine. In the temperature range 423–573 K, the delayed fluorescence quenching rate constants k _q are estimated from changes in the decay rate constant and the intensity of delayed fluorescence upon increasing pressure of bath gases. It is ascertained that, in the gas phase, the mixtures under study exhibit both a negative and a positive dependence of k _q on temperature, which indicates that some photoinduced reactions do not have activation barriers. The rate constant k _q is shown to increase with decreasing ionization potential of the electron donors. This points to the importance of interactions with charge transfer in the photoreaction of triplet ketone molecules with aliphatic amines and pyridine in the gas phase. The relationship between k _q and the change in the free energy ΔG upon the photoinduced intermolecular electron transfer, which is the primary stage of the photochemical reaction, is studied. It is shown that the dependence k _q (ΔG) for the donor-acceptor pairs under study is described well by the Marcus equation, in which the average vibrational energies of the donor and acceptor are taken into account for the estimate of ΔG.     

Intramolecular energy transfer by singlet and triplet excitons in macromolecules

Absorption, luminescence and photo-oxidation of polyvinylcarbazole (PVCa) and polyvinylbenzocarbazole (PVBCa) in weak solutions have been studied. It is found that fluorescence and phosphorescence spectra, observed at 293, 77 and 4.2 K, depend on the molecular mass M of the polymer and on the experimental conditions. Due to efficient intramolecular energy transfer the fluorescence spectrum includes the emission of excimers, emission of end groups and that of internal structural defects of a macrochain. The relative role of each emission markedly depends on M. Phosphorescence is largely determined by the annihilation effects between triplet excitations, these effects being pronounced in long macrochains. The data show the excitonic nature of the singlet and triplet excitation energy transfer in the polymers studied. The migration of one-dimensional singlet and triplet excitons strongly influences the luminescent properties of PVCa and PVBCa macromolecules, as well as their photochemical reactions. The range of singlet excitons in PVCa and PVBCa macromolecules is determined both at room temperature and at low temperatures.     

Effect of cascading of higher-lying states on a delayed 1s-2p transition after beam-foil excitation of 56 MeV hydrogen-like oxygen and fluorine

The delayed fluorescence of the soft X-ray (1s-2p) transition was observed for H-like ions (O⁷⁺ and F⁸⁺) between 1.3 ns and 20 ns decay time after beam-foil excitation. The delayed X-ray fluorescence was found to decay with at ^Δ power law time dependence. The non-exponential decay is attributed to cascading through higher lying states. We found thatΔ ₀=1.40±0.08 andΔ _F =1.44±0.02 for H-like oxygen and fluorine, respectively. Present results are in fair agreement with the previously reported exponent,Δ ₀=1.5, measured over 3 ns after excitation.     

Time-dependent Schrödinger approach to sub-barrier fission

The time-dependent Schrödinger equation for the fission of²¹³At through a one-dimensional potential barrier was solved numerically within a finite spatial grid. Several initial quasi-stationary vibrational states at and below the top of the barrier were considered. The time dependence of the decay rate γ(t) was calculated. The non-exponential evolution of the process in the very early stages (≦10^?20 s) differs considerably from the asymptotic (stationary) one. Fission is therefore delayed by the sum of this preexponential time, of the tunneling time and of the time necessary for the descent from the outer turning point to the scission point. These non-dissipative quantum times play the same role as the classical transient times usually included in the analyses of experimental data on pre-scission emission of light particles andγ rays.     

Electrical and thermal properties of a-(Se70Te30)100−x(Se98Bi2)x (0⩽x⩽20) alloys

In electrical properties, the dc conductivity and photoconductivity measurements have been made in vacuum evaporated thin films of a-(Se₇₀Te₃₀)_100−x(Se₉₈Bi₂)_x system, in the temperature range (308–355 K). It has been observed that dc conductivity and activation energy depend on the Bi concentration. Photocurrent dependence on incident radiation has also been observed which follow the power law (I_ph∝F^γ). Transient photocurrent exhibits the non-exponential decay time. All these parameters show that the recombination within the localized states is predominant. In crystallization kinetics, the heating rate dependence of glass transition and crystallization temperatures is studied to calculate the activation energy for thermal relaxation and activation energy for crystallization. The composition dependence of the activation energy for thermal relaxation and activation energy for crystallization is discussed in terms of the structure of Se–Te–Bi glassy system.