Electronic system excitation process

To make QM studies of chemical reactions in the condensed phase computationally more feasible combined quantum me-chanical/molecular mechanical (QM/MM) methods have been developed. The idea of combined QM/MM methods, introduced first by Levitt and Warshell [17] in 1976, is to divide the system into a part which is treated accurately by means of quantum mechanics and a part whose properties are approximated by use of QM methods (Fig. 5.1). Typically, QM methods are used to describe chemical processes in which bonds are broken and formed, or electron-transfer and excitation processes, which cannot be treated with MM methods. Combined QM and MM methods have been extensively used to study chemical reactions in solution and the mechanisms of enzyme-catalyzed reactions. When the system is partitioned into the QM and MM parts it is assumed that the process requiring QM treatment is localized in that region. The MM methods are then used to approximate the effects of the environment on the QM part of the system, which, via steric and electrostatic interactions, can be substantial. The... 

It can be seen from the normal potentials E° (see p. 18) of the most important redox systems involved in the light reactions why two excitation processes are needed in order to transfer electrons from H2O to NADP"". After excitation in PS II, E° rises from around -IV back to positive values in plastocyanin (PC)—i. e., the energy of the electrons has to be increased again in PS I. If there is no NADP" available, photosynthetic electron transport can still be used for ATP synthesis. During cyclic photophosphorylation, electrons return from ferredoxin (Fd) via the plastoquinone pool to the b/f complex. This type of electron transport does not produce any NADPH, but does lead to the formation of an gradient and thus to ATP synthesis. 

In Part II we discussed how to measure the electrical parameters n and pn (and/or p and pp), namely, by means of the conductivity and Hall coefficient. Now we must ask how these parameters relate to the more fundamental quantities of interest, such as impurity concentrations and impurity activation energies. Much can be learned from a consideration of thermal excitation processes only, i.e., processes in which the only variable parameter is temperature. Thus, we are specifically excluding cases involving electron or hole injection by high electric fields or by light. We are also excluding systems that have been perturbed from their thermal equilibrium state and have not yet had sufficient time to return. Some of these nonequilibrium situations will be considered in Part IV. 

In any allowed electronic energy transfer process, the overall spin angular momentum of the system should not change. This statement is known as Wigner s spin conservation rule. The rule is applicable whether the transfer occurs between an excited atom or a molecule and another molecule in its ground state or in the excited state. In an electronic transition between the energy states of the same molecule also, spin is necessarily conserved. But the phenomenon is governed by rules for dipole-dipole interaction. 

In what follows we shall consider an excitation process which is short lived on the time scale of the resulting excited state. This excitation process may involve an electron-molecule collision or absorption of a light pulse. We start with the system in the ground state (f>0. The excitation process introduces a time-dependent perturbation Tx(t) for a duration of time r. An excited nonstationary state is thereby produced which can be represented as a superposition of molecular eigenstates (see eq. 6-2)... 

Compared with the momentum of impinging atoms or ions, we may safely neglect the momentum transferred by the absorbed photons and thus we can neglect direct knock-on effects in photochemistry. The strong interaction between photons and the electronic system of the crystal leads to an excitation of the electrons by photon absorption as the primary effect. This excitation causes either the formation of a localized exciton or an (e +h ) defect pair. Non-localized electron defects can be described by planar waves which may be scattered, trapped, etc. Their behavior has been explained with the electron theory of solids [A.H. Wilson (1953)]. Electrons which are trapped by their interaction with impurities or which are self-trapped by interaction with phonons may be localized for a long time (in terms of the reciprocal Debye frequency) before they leave their potential minimum in a hopping type of process activated by thermal fluctuations. 

In recent years there has been a considerable amount of research on transition metal complexes due to the large number of potential or already realized technical applications such as solar energy conversion through photo-redox processes, optical information and storage systems, photolithographic processes, etc. Moreover, metal complexes are also of considerable importance in biology and medicine. Most of these applications are directly related to the electronic and vibronic properties of the ground and lowest excited states. 

In this chapter we consider inelastic collisions of positrons with an atomic or molecular target X which result in electronic excitation or ionization (without positronium formation) of the target system. These processes can be summarized as... 

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