Modelling Photochemical Reactivity of Organic Systems — A New Challenge to Quantum Computational Chemistry

AbstractThe applicability of modern methods of quantum computational chemistry to the problem of modelling photochemical mechanisms is discussed. It is demonstrated that one of the central mechanistic features is the surface‐crossing region which takes the form of a conical intersection. It is shown that this mechanistic feature can yield a new rationalization of common experimental observations such as the simultaneous production of different photoproducts, the occurrence of rigid stereochemistry, and the occurrence of very low fluorescence quantum yields. In addition, a simple VB model can often lead to accurate predictions about the nature of the surface‐crossing region and the nature of the recoupling pathways on the ground‐state surface.