Energy-transfer processes

In this chapter we shall first outline the basic concepts of the various mechanisms for energy redistribution, followed by a very brief overview of collisional intennoleciilar energy transfer in chemical reaction systems. The main part of this chapter deals with true intramolecular energy transfer in polyatomic molecules, which is a topic of particular current importance. Stress is placed on basic ideas and concepts. It is not the aim of this chapter to review in detail the vast literature on this topic we refer to some of the key reviews and books [U, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, and 32] and the literature cited therein. These cover a variety of aspects of tire topic and fiirther, more detailed references will be given tliroiighoiit this review. We should mention here the energy transfer processes, which are of fiindamental importance but are beyond the scope of this review, such as electronic energy transfer by mechanisms of the Forster type [33, 34] and related processes. 

The fimdamental kinetic master equations for collisional energy redistribution follow the rules of the kinetic equations for all elementary reactions. Indeed an energy transfer process by inelastic collision, equation (A3.13.5). can be considered as a somewhat special reaction . The kinetic differential equations for these processes have been discussed in the general context of chapter A3.4 on gas kmetics. We discuss here some special aspects related to collisional energy transfer in reactive systems. The general master equation for relaxation and reaction is of the type [H, 12 and 13, 15, 25, 40, 4T ] ... 

Note that in the low pressure limit of iinimolecular reactions (chapter A3,4). the unimolecular rate constant /fu is entirely dominated by energy transfer processes, even though the relaxation and incubation rates... 

The master equation treatment of energy transfer in even fairly complex reaction systems is now well established and fairly standard [ ]. However, the rate coefficients kjj or the individual energy transfer processes must be established and we shall discuss some aspects of this matter in tire following section. 

Given such a reference, we can classify various mechanisms of energy transfer either by the probability tiiat a certain energy transfer process will occur in a Leimard-Jones reference collision , or by the average energy transferred by one Leimard-Jones collision . 

With this convention, we can now classify energy transfer processes either as resonant, if IA defined in equation (A3.13.81 is small, or non-resonant, if it is large. Quite generally the rate of resonant processes can approach or even exceed the Leimard-Jones collision frequency (the latter is possible if other long-range potentials are actually applicable, such as by pennanent dipole-dipole interaction). 

In the experimental and theoretical study of energy transfer processes which involve some of the above mechanisms, one should distingiush processes in atoms and small molecules and in large polyatomic molecules. For small molecules a frill theoretical quantum treatment is possible and even computer program packages are available [, and ], with full state to state characterization. A good example are rotational energy transfer theory and experiments on Fie + CO [M] ... 

Steinfeld J I and Klemperer W 1965 Energy-transfer processes in monochromatically excited iodine molecules. I. Experimental resulted. Chem. Phys. 42 3475-97... 

CFIDF end group, no selective reaction would occur on time scales above 10 s. Figure B2.5.18. In contrast to IVR processes, which can be very fast, the miennolecular energy transfer processes, which may reduce intennolecular selectivity, are generally much slower, since they proceed via bimolecular energy exchange, which is limited by the collision frequency (see chapter A3.13). 

Almost all aspects of the field of chemistry involve tire flow of energy eitlier witliin or between molecules. Indeed, tire occurrence of a chemical reaction between two species implies tire availability of some minimum amount of energy in tire reacting system. The study of energy transfer processes is tluis a topic of fundamental importance in chemistry. Energy transfer in gases is of particular interest partly because very sophisticated methods have been developed to study such events and partly because gas phase processes lend tliemselves to very complete and detailed tlieoretical analysis. 

The evidence in Figure 2 for a kinetic energy threshold for reaction of excited H2+ with He does not support the assumption of a kinetic energy transfer process for the excitation of reactant H2+ with v < 5 in reactive collisions with He. If such processes were probable, a drastic change in the maximum value of Q or k might be expected. The transfer of less than 0.5 e.v. of kinetic to internal energy would add quantum states with v = 3 and 4 to the inventory of available H2 + reactant and increase the maximum value of k by a factor of 2. 

Depending on the relative concentration of reactive substrate and dissolved molecular oxygen ( 02), RF is able to induce photosensitized oxidation of molecular targets by either Type I (electron-transfer) or Type II (energy-transfer) processes (Foote, 1991). In Type I... 

The LIF technique is extremely versatile. The determination of absolute intermediate species concentrations, however, needs either an independent calibration or knowledge of the fluorescence quantum yield, i.e., the ratio of radiative events (detectable fluorescence light) over the sum of all decay processes from the excited quantum state—including predissociation, col-lisional quenching, and energy transfer. This fraction may be quite small (some tenths of a percent, e.g., for the detection of the OH radical in a flame at ambient pressure) and will depend on the local flame composition, pressure, and temperature as well as on the excited electronic state and ro-vibronic level. Short-pulse techniques with picosecond lasers enable direct determination of the quantum yield [14] and permit study of the relevant energy transfer processes [17-20]. 

BiUter, A. et al.. Study of energy transfer processes in CH as prerequisite for quantitative minor species concentration measurements, Appl. Phys. B, 79,113,2004. 

Another class of photochemically relevant polyphosphazenes is formed by macromolecules having chromophores able to absorb light in a selective way and to transfer it to external species, thus inducing different reactions by energy transfer processes. In some cases electron transfer processes are also involved. These situations are described by Formula below and the corresponding polymers and external reagents are reported in Table 26. 

Similarly, energy-transfer processes, together with electron transfer and hydrogen abstraction reactions could be induced in poly(organophosphazenes) in an intramolecular way by preparing POPs geminally substituted at the same phosphorus with two different substituent groups. 

Hydroxy Benzophenone P-Naphthoxy Energy Transfer Processes Self-Stabilized Polymers" ... 

In dichloromethane solutions, excitation of the chromophoric groups of the dendrons causes singlet-singlet energy transfer processes that lead to the excitation of the porphyrin core. It was found that the dendrimer 17, which has a spherical morphology, exhibits a much higher energy transfer quantum yield (0.8) than the partially substituted species 13-16 (quantum yield <0.32). Fluo-... 

Figure 17.12 (A) Schematic presentation of deactivation and energy transfer processes in a single quantum dot placed on an Ag nanoparticle film. (B) Photoluminescence intensity trajectories of single quantum dots on a glass substrate (a) and on an Ag nanoparticle film (b). The traces in green represent background intensities. (C) Photoluminescence spectra of quantum dot solutions in the presence of...

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