Nonradiative processes

The easiest method for creating many vibrational excitations is to use convenient pulsed visible or near-UV lasers to pump electronic transitions of molecules which undergo fast nonradiative processes such as internal conversion (e.g. porjDhyrin [64, 65] or near-IR dyes [66, 62, 68 and 62]), photoisomerization (e.g. stilbene [12] or photodissociation (e.g. Hgl2 [8]). Creating a specific vibrational excitation D in a controlled way requires more finesse. The easiest method is to use visible or near-UV pulses to resonantly pump a vibronic transition (e.g. 

This confinement yields a higher carrier density of elections and holes in the active layer and fast ladiative lecombination. Thus LEDs used in switching apphcations tend to possess thin DH active layers. The increased carrier density also may result in more efficient recombination because many nonradiative processes tend to saturate. The increased carrier confinement and injection efficiency faciUtated by heterojunctions yields increasing internal quantum efficiencies for SH and DH active layers. Similar to a SH, the DH also faciUtates the employment of a window layer to minimise absorption. In a stmcture grown on an absorbing substrate, the lower transparent window layer may be made thick (>100 /tm), and the absorbing substrate subsequendy removed to yield a transparent substrate device. 

The requited characteristics of dyes used as passive mode-locking agents and as active laser media differ in essential ways. For passive mode-locking dyes, short excited-state relaxation times ate needed dyes of this kind ate characterized by low fluorescence quantum efficiencies caused by the highly probable nonradiant processes. On the other hand, the polymethines to be appHed as active laser media ate supposed to have much higher quantum efficiencies, approximating a value of one (91). 

For a simplified case, one can obtain the rate of CL emission, =ft GI /e, where /is a function containing correction parameters of the CL detection system and that takes into account the fact that not all photons generated in the material are emitted due to optical absorption and internal reflection losses q is the radiative recombination efficiency (or internal quantum efficiency) /(, is the electron-beam current and is the electronic charge. This equation indicates that the rate of CL emission is proportional to q, and from the definition of the latter we conclude that in the observed CL intensity one cannot distii pish between radiative and nonradiative processes in a quantitative manner. One should also note that q depends on various factors, such as temperature, the presence of defects, and the... 

As mentioned above, the interpretation of CL cannot be unified under a simple law, and one of the fundamental difficulties involved in luminescence analysis is the lack of information on the competing nonradiative processes present in the material. In addition, the influence of defects, the surface, and various external perturbations (such as temperature, electric field, and stress) have to be taken into account in quantitative CL analysis. All these make the quantification of CL intensities difficult. Correlations between dopant concentrations and such band-shape parameters as the peak energy and the half-width of the CL emission currently are more reliable as means for the quantitative analysis of the carrier concentration. 

Figure 3. Energy diagram for 1064 nm excitation of PuFg(g). The 5f electron states of PuF6 are shown at the left. The solid arrows Indicate photon absorption or emission processes. The wavy arrows indicate nonradiative processes by which excited states of PuF6 are lost. Comparison of observed fluorescence photon yields versus the fluorescence quantum yield expected for the 4550 cm" state indicate that the PuFg state initially populated following 1064 nm excitation may dissociate as shown.

Thus if one starts with one pure isomer of a substance, this isomer can undergo first-order transitions to other forms, and in turn these other forms can undergo transitions among themselves, and eventually an equilibrium mixture of different isomers will be generated. The transitions between atomic and molecular excited states and their ground states are also mostly first-order processes. This holds both for radiative decays, such as fluorescence and phosphorescence, and for nonradiative processes, such as internal conversions and intersystem crossings. We shall look at an example of this later in Chapter 9. 

Two important factors that influence the rate of these nonradiative processes are ... 

The efficiency of these radiative processes often increase at low temperatures or in solvents of high viscosity. Consequently emission spectra are generally run in a low-temperature matrix (glass) or in a rigid polymer at room temperature. The variation in efficiency of these processes as a function of temperature and viscosity of the medium indicates that collisional processes compete with radiative and unimolecular nonradiative processes for deactivation of the lowest singlet and triplet states. 

The effect of the substitution of a heavy-atom directly onto the nucleus of aromatic compounds (internal heavy-atom effect) on intercombinational radiative and nonradiative processes can be seen by examination of experimental data obtained for naphthalene and its derivatives. The data obtained by Ermolaev and Svitashev<104) and analyzed by Birks(24) to obtain individual rate constants for the various processes are collected in Table 5.9. 

Let us now consider a molecule A in the solid phase of a given crystalline modification. Irradiation of this crystalline phase leads to excitation of A to its first excited singlet state, which can (a) react to give product, (b) decay to the ground state by radiative or nonradiative processes, (c) undergo intersystem crossing to the triplet, which can (1) react to give product, or (2) decay to... 

FRET is a nonradiative process that is, the transfer takes place without the emission or absorption of a photon. And yet, the transition dipoles, which are central to the mechanism by which the ground and excited states are coupled, are conspicuously present in the expression for the rate of transfer. For instance, the fluorescence quantum yield and fluorescence spectrum of the donor and the absorption spectrum of the acceptor are part of the overlap integral in the Forster rate expression, Eq. (1.2). These spectroscopic transitions are usually associated with the emission and absorption of a photon. These dipole matrix elements in the quantum mechanical expression for the rate of FRET are the same matrix elements as found for the interaction of a propagating EM field with the chromophores. However, the origin of the EM perturbation driving the energy transfer and the spectroscopic transitions are quite different. The source of this interaction term... 

Photon emission must be a favorable deactivation process of the excited product in relation to other competitive nonradiative processes that may appear in low proportion (Fig. 3). In the case of sensitized CL, both the efficiency of energy transfer from the excited species to the fluorophore and the fluorescence efficiency of the latter must be important. 

The nonradiative processes immediately leading to and competing with light emission... 

As a rule, however, most of the ESIPT dyes exhibit weak to very weak fluorescence quantum yields, i.e., the quantum yield of the nonradiative processes is near unity. Such dyes, if they show little permanent photodestruction, can be used as ultraviolet (UV)-stabilizers of polymers, such as Tinuvin (a hydroxy-benzotria-zole),(45) because they efficiently convert UV radiation, harmful for the polymer, into harmless heat. The mechanisms of these nonradiative decay paths are often linked to... 

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