No label defined (Q4451067)

The book presents a review of approximate methods in quantum theory which are based on classical picture as a zero approximation. The author prefers the term ''quantum-classical'' for the whole scope of the methods including the early ones (called now classical path theories), reserving the term ''semi-classical'' for the methods developed later, such as classical S-matrix theory, WKB theories, and others. Some of the quantum-classical methods presented in the book have been successfully used to treat a large body of molecular events: inelasic processes, energy transfer, collision induced dissociation, as well as photo-dissociation chemical reactions, and non-adiabatic electronic processes. Some of the results reviewed in the book have not been published previously. After a short Introduction containing particularly a classification of the quantum-classical methods, the author reviews in Chapter 2 the underlying rigorous theories such as path-integral approach, theory of Gaussian wave packets, bound states, second quantization and quantum dressed classical mechanics. After this, in Chapter 3 he reviews the simplest approximate theories. After formulating requirements for approximate dynamical calculations, the method of self-consistent field is sketched which, according to the author, obtained a reputation as the ''poor man's quantum mechanics'' but is in fact much more efficient than this reputation would indicate. Then the next approximate method, the classical path theory, is presented in more details. It is based on treating some degrees of freedom classically, others quanum mechanically, with the interaction between the two sets of degrees of freedom accounted for in a simplified and often ad hoc manner. Typically, nuclei are treated classically whereas the electronic motion is quantized. A collinear collision between an atom and a diatomic molecule, diatom-diatom collision, and collision of hydrogen with He atoms are considered with the help of this method, and the results obtained in the classical path approximation are compared with those given by precise quantum calculations. The classical path approach is compared with other theories such as eikonal approach and some WKB-type theories derived in the seventies. It is shown how chemical reactions may be accounted in the process of scattering with the help of the primitive quantum-classical theory, provided that the coordinates are chosen properly. At the end of Chapter 3 non-adiabatic electronic transitions are considered in the approximation where the dynamics of the nuclei are treated classically and the electrons are quantized. In Chapter 4, the concept of second quantization, introduced in Chapter 2 as a general tool for treating excitation in molecular collisions, is considered in more detail. It is shown how this concept may be efficiently used in various dynamical situations, as for instance when dealing with the vibrational excitation of diatomic and polyatomic molecules, or with energy transfer to solids and chemical reactions in the so-called reaction path formulation. Since the formal expressions in the operators are the same, irrespective of the system or dynamical situation, the algebraic manipulations are also identical, and, hence, the formal solution the same. More complex systems are considered in Chapter 5. By more complex systems, those are meant which contain hundreds or thousands of atoms, or those containing less atoms but more complicated motions (e.g. collisions between polyatomic molecules). The quantum-classical methods are considered allowing to treat energy transfer in collisions involving polyatomic molecules, molecule surface scattering, reactions in polyatomic systems and solution. It is assumed that a realistic potential energy surface may be empirically or semi-empirically constructed for the system under consideration. Summarizing, this rather compact book gives a sufficiently general outlook on the approaches applicable to complicated, first of all molecular, quantum systems. It will be useful for theorists working in the areas of quantum chemistry and condensed state physics.