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WIREs Comput Mol Sci
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Spin–orbit coupling and intersystem crossing in molecules

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Abstract Many light‐induced molecular processes involve a change in spin state and are formally forbidden in non‐relativistic quantum theory. To make them happen, spin–orbit coupling (SOC) has to be invoked. Intersystem crossing (ISC), the nonradiative transition between two electronic states of different multiplicity, plays a key role in photochemistry and photophysics with a broad range of applications including molecular photonics, biological photosensors, photodynamic therapy, and materials science. Quantum chemistry has become a valuable tool for gaining detailed insight into the mechanisms of ISC. After a short introduction highlighting the importance of ISC and a brief description of the relativistic origins of SOC, this article focusses on approximate SOC operators for practical use in molecular applications and reviews state‐of‐the‐art theoretical methods for evaluating ISC rates. Finally, a few sample applications are discussed that underline the necessity of studying the mechanisms of ISC processes beyond qualitative rules such as the El‐Sayed rules and the energy gap law. © 2011 John Wiley & Sons, Ltd. This article is categorized under: Structure and Mechanism > Molecular Structures

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