MULTI-ELECTRONIC-STATE MOLECULAR-DYNAMICS - A WAVE-FUNCTION APPROACH WITH APPLICATIONS

An approach which allows for multi-electronic-state dynamics but which is in the spirit of classical molecular dynamics is discussed and app lied to both collisional (''curve crossing'') and ultrafast optical ex citation problems. The formalism seeks to allow for the possibility of quite different nuclear dynamics (e.g., bound vs dissociative) in the different electronic states. The discussion begins from a wave functi on formulation of the problem, and this enables one to retain interfer ence effects if these are important, but the ultimate objective is to obtain as classical-like a description as possible while taking accoun t of the inter-electronic state coupling. The essential approximation in the method is in the computation of these coupling terms which appe ar as nonclassical corrections to the classical equations of motion. T he computational results are tested against accurate quantal computati ons, and the agreement is typically quantitative.