Phosphorescence decay rate

From the practical point of view, the radiative decay rate kr may be assumed to be independent of the external parameters surrounding the excited sensor molecule. Its value is determined by the intrinsic inability of the molecule to remain in the excited state. The radiative decay rate kr is a function of the unperturbed electronic configuration of the molecule. In summary, for a given luminescent molecule, its unperturbed fluorescent or phosphorescent decay rate (or lifetime) may be regarded to be only a function of the nature of the molecule. 

Temperature, pressure and deuterium effects on the phosphorescence decay-rate constant of naphthalene in single crystals of durene show that photo-induced hydrogen abstraction... 

One may not generally assume (vide infra) that there is no temperature dependence of the total decay rates so should not be obtained from the high temperature (i. e. 77 °K) phosphorescence decay rate. 

Figure4.7 (a) Normalized phosphorescence spectra at 10 l< and absorption spectra at 300 l< of the Pt-containing polymer (solid line) and its monomer (dotted line). The inset shows the chemical structures of the polymer and monomer, (b) Arrhenius plot of the phosphorescence decay rate against the inverse temperature. The black curves correspond to the equation...

This method is illustrated in Figure 2.7, which shows the variation of the phosphorescence decay rate of 1-bromonaph-thalene solubilized in sodium dodecylsulfate (SDS) micelles in the presence of an increasing concentration of sodium nitrite in the aqueous phase. The 1-bromonaphthalene triplet... 

For pyrazine three exponential decays of lifetime 6, 130, and 400 msec can be extracted. From these three values the 77°K rate constant for phosphorescence decay can be calculated ... 

The fluorescence and phosphorescence of luminescent materials are modulated by the characteristics of the environment to which these materials are exposed. Consequently, luminescent materials can be used as sensors (referred also as transducers or probes) to measure and monitor parameters of importance in medicine, industry and the environment. Temperature, oxygen, carbon dioxide, pH, voltage, and ions are examples of parameters that affect the luminescence of many materials. These transducers need to be excited by light. The manner in which the excited sensor returns to the ground state establishes the transducing characteristics of the luminescent material. It is determined by the concentration or value of the external parameter. A practical and unified approach to characterize the luminescence of all sensors is presented in this chapter. This approach introduces two general mechanisms referred as the radiative and the nonradiative paths. The radiative path, in the general approach, is determined by the molecular nature of the sensor. The nonradiative path is determined by the sensor environment, e.g., value or concentration of the external parameter. The nonradiative decay rate, associated with the nonradiative path, increases... 

The long lifetime has important consequences on the decay rates. First, we consider what affects the nonradiative rates (knr) which change the yields of fluorescence and phosphorescence. The nonradiative decay rate is often enhanced in molecules which have flexible constituents (the so-called loose-bolt effect). Therefore, both fluorescence and phosphorescence yields are generally larger for rigid molecules than flexible molecules. For the same reason, a rigid environment will increase the emission yields hence both fluorescence and phosphorescence yields often increase with increasing viscosity. 

It has been observed that for some proteins the room temperature phosphorescence lifetimes are increased in D20. The phosphorescence lifetime of liver alcohol dehydrogenase is 300 ms in H2Oand 500 ms in D2O.<10) Phosphorescence lifetimes are often dramatically increased by exchanging hydrogen with deuterium. The reason for this is that decay rates are affected by overtones of the C-H or N-H stretch. In the case of tryptophan in... 

There are established techniques for the determination of and np (Section 10.2). In this expression, kf and kp are reciprocals of the radiative lifetimes of flucrescene and phosphorescence states, respectively, kf can be obtained experimentally from the integrated area under the absorption curve and kp is obtained from the measured decay rates for phosphorescence at 77K in EPA. In Table 5.3 the observed quantities, their symbols, relation to rate constants and sources of studies are summarized. 

The lifetime of triplet acetone at 25° in the vapor phase, as measured from the rate of decay of phosphorescence, is 0.0002 sec,318 so that the rate of decay is 5 x 103 sec-1. This figure represents the sum of the rates of all decay processes. Since the data at 40° 308 indicate that decomposition and internal conversion of triplet acetone occur approximately 40 times as fast as emission, the radiative lifetime must be on the order of 0.01 sec. Measurements of the rate of phosphorescence decay from solid acetone at 77°K, where all activated fragmentation and most radiationless decay normally disappear, have actually yielded values approximately one-tenth as large as that obtained in the gas phase at room temperature.319 The most recent measurements of the lifetime of triplet acetone at 77°K in frozen glasses does indeed yield an estimate of 0.01 sec for the radiative lifetime of triplet acetone.318... 

Electron transfer kinetics from the triplet excited state of TMPD to PA in polystyrene has been monitored by phosphorescence emission decay in ref. 85. The rate constant has been found to be invariant over the temperature interval 77-143 K. Parameters ae and ve calculated from the phosphorescence decay using eqn. (12) were found to be ae = 3.46 A and vc = 104 s 1. 

The optical and PL spectroscopies have been undertaken to understand the structure-property correlations of this important family of triplet-emitting polymers. The red shift in the absorption features upon coordination of the metal groups is consistent with there being an increase in conjugation length over the molecule through the metal center. The trade-olf relationship between the phosphorescence parameters (such as emission wavelength, quantum yield, rates of radiative and nonradiative decay) and the optical gap will be formulated. For systems with third-row transition metal chromophores in which the ISC efficiency is close to 100%,76-78 the phosphorescence radiative (kr)y, and nonradiative (/cm)p decay rates are related to the measured lifetime of triplet emission (tp) and the phosphorescence quantum yield ([Pg.300]

Confirmation that the emitting species in phosphorescent organic molecules is a triplet has come from several sources. In the 1940s it was discovered that a solution of fluorescein in boric acid glass became paramagnetic under intense irradiation more recently it has been shown that the paramagnetism and the phosphorescence decay at identical rates when irradiation ceases. The electron paramagnetic resonance (EPR) technique is capable of detect-... 

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