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Femtosecond Photoelectron imaging as a Probe for Non-Adiabatic Evolution

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Abstract

Electronic energy relaxation in large molecules is an ubiquitous phenomenon which ensures their photostability by transforming the electronic energy into internal energy of the ground electronic state. This is essential in biological systems exposed to light. The electronic energy is rapidly degraded and thermalized within the ground electronic state of these systems, preventing most of the photochemistry through dissipation of the energy in the medium. These properties arise from change between the electronic configurations of the molecular systems accessible by optical excitation, and other energetically accessible configurations, through conical intersections, a mechanism that funnels the system through various excited surfaces. This process provides a direct descent to the lowest energy surface guided by the gradients along these surfaces. Ethylene has long been recognized as being a model system for this relaxation and we shall describe here experiments on a substituted ethylene as in the insert.

© 2005 Optical Society of America

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