Energy-transfer Reactions

Figure 19.1 Mechanisms involved in sunlight-induced phototoxicity of drugs. Type 1 photosensitization (electron transfer) mainly generates singlet oxygen Oj", whereas type 2 reaction (energy transfer) leads to adduct formation or singlet oxygen...

Quenching.—Any deactivation of an excited state (but not necessarily to the ground state) by interaction with other components of the system, which prevents some otherwise observable process such as emission or chemical reaction. Energy transfer is always involved but the detailed mechanisms may vary considerably. 

Very low pressure pyrolysis (vlpp). It is possible to use pressures in flow systems that are very much lower than those in static systems. In vlpp systems the pressures are of the order of 10 -10" torr. Previous work has been reviewed and the technique highlighted by Benson and Spokes . Here energy transfer is predominantly via gas-wall collisions. The method provides a new kinetic tool for a detailed study of unimolecular reactions, energy transfer, bimolecular gaseous reactions and heterogeneous reactions . The reactant flows from a 51 reservoir... 

Atomic and Molecular Collisions Coherent Control of Chemical Reactions Energy Transfer, Intramolecular Ion Kinetics and Energetics Kinetics, Chemical Molecular Beam Epitaxy, Semiconductors... 

Bioenergetics Electron Transfer Reactions Energy Transfer, Intramolecular Ion Kinetics AND Energetics Ion transport Across Biological Membranes Lipoprotein/Cholesterol Metabolism Protein Synthesis... 

Quack M and Troe J 1977 Unimoiecuiar reactions and energy transfer of highiy excited moiecuies Gas Kinetios and Energy Transfervo 2 (London The Chemicai Society)... 

This is no longer the case when (iii) motion along the reaction patir occurs on a time scale comparable to other relaxation times of the solute or the solvent, i.e. the system is partially non-relaxed. In this situation dynamic effects have to be taken into account explicitly, such as solvent-assisted intramolecular vibrational energy redistribution (IVR) in the solute, solvent-induced electronic surface hopping, dephasing, solute-solvent energy transfer, dynamic caging, rotational relaxation, or solvent dielectric and momentum relaxation. 

Kajimoto O 1999 Soivation in supercriticai fluids its effects on energy transfer and chemicai reactions Chem. Rev. 99 355-89... 

For example, energy transfer in molecule-surface collisions is best studied in nom-eactive systems, such as the scattering and trapping of rare-gas atoms or simple molecules at metal surfaces. We follow a similar approach below, discussing the dynamics of the different elementary processes separately. The surface must also be simplified compared to technologically relevant systems. To develop a detailed understanding, we must know exactly what the surface looks like and of what it is composed. This requires the use of surface science tools (section B 1.19-26) to prepare very well-characterized, atomically clean and ordered substrates on which reactions can be studied under ultrahigh vacuum conditions. The most accurate and specific experiments also employ molecular beam teclmiques, discussed in section B2.3. 

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 ] ... 

In equation (A3.13.24), /c. is the specific rate constant for reaction from level j, and are energy transfer... 

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. 

Collisional energy transfer in molecules is a field in itself and is of relevance for kinetic theory (chapter A3.1). gas phase kmetics (chapter A3.4). RRKM theory (chapter A3.12). the theory of unimolecular reactions in general,... 

The standard mechanisms of collisional energy transfer for both small and large molecules have been treated extensively and a variety of scaling laws have been proposed to simplify the complicated body of data [58, 59, 75]. To conclude, one of the most efficient special mechanisms for energy transfer is the quasi-reactive process involving chemically bound intennediates, as in the example of the reaction ... 

Quack M and Tree J 1976 Unimolecular reactions and energy transfer of highly excited molecules Gas Kinetics and Energy Transfer mo 2, oh 5, ed P G Ashmore and R J Donovan (London The Chemical Society) pp 175-238 (a review of the literature published up to early 1976)... 

Venkatesh P K, Dean A M, Cohen M H and Carr R W 1999 Master equation analysis of intermolecular energy transfer in multiple-well, multiple-channel unimolecular reactions. II. Numerical methods and application to the mechanism of the C. + O2 reaction J. Chem. Phys. Ill 8313... 

Once the excited molecule reaches the S state it can decay by emitting fluorescence or it can undergo a fiirtlier radiationless transition to a triplet state. A radiationless transition between states of different multiplicity is called intersystem crossing. This is a spin-forbidden process. It is not as fast as internal conversion and often has a rate comparable to the radiative rate, so some S molecules fluoresce and otliers produce triplet states. There may also be fiirther internal conversion from to the ground state, though it is not easy to detemiine the extent to which that occurs. Photochemical reactions or energy transfer may also occur from S. ... 

Jean J M, Chan C-K and Fleming G R 1988 Electronic energy transfer in photosynthetic bacterial reaction centers Isr. J. Chem. 28 169-75... 

Stanley R J, King B and Boxer S G 1996 Excited state energy transfer pathways in photosynthetic reaction centers. 1. Structural symmetry effected. Phys. Chem. 100 12 052-9... 

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. 

With tlie development of femtosecond laser teclmology it has become possible to observe in resonance energy transfer some apparent manifestations of tire coupling between nuclear and electronic motions. For example in photosyntlietic preparations such as light-harvesting antennae and reaction centres [32, 46, 47 and 49] such observations are believed to result eitlier from oscillations between tire coupled excitonic levels of dimers (generally multimers), or tire nuclear motions of tire cliromophores. This is a subject tliat is still very much open to debate, and for extensive discussion we refer tire reader for example to [46, 47, 50, 51 and 55]. A simplified view of tire subject can nonetlieless be obtained from tire following semiclassical picture. 

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