Abstract
Chemistry that takes place exclusively in the ground electronic state can be well described by a reaction path in which the reactants pass over a transition state to the products. After photoexcitation, a molecule is in an excited electronic state and new topographical features joining different states, known as conical intersections, also need to be considered to describe the time-evolution from reactants to products. These intersections are due to the coupling between electrons and nuclei. In addition to providing new pathways, they provide a quantum-mechanical phase to the system which means that to describe the nuclear motion properly methods are required that include the resulting quantum-mechanical coherences in the nuclear motion. In this chapter, we review the nature and topography of conical intersections and simulation methods that have been developed to describe a molecule passing through one. These range from the full solution of the time-dependent Schrödinger equation to approximate methods based on Newtonian mechanics. Using examples the advantages and disadvantages of each are discussed.
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Lasorne, B., Worth, G.A., Robb, M.A. (2014). Non-adiabatic Photochemistry: Ultrafast Electronic State Transitions and Nuclear Wavepacket Coherence. In: Gatti, F. (eds) Molecular Quantum Dynamics. Physical Chemistry in Action. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-45290-1_7
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DOI: https://doi.org/10.1007/978-3-642-45290-1_7
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