Conical Intersections and the Spin‐Orbit Interaction

Matsika, Spiridoula; Yarkony, David R.

doi:10.1002/0471433462.ch10

Cited by 10 publications

(6 citation statements)

References 25 publications

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“…To locate the point of intersection in an even‐electron molecule, a two‐dimensional branching plane must be searched. The situation is even more involved for odd‐electron molecules since the branching space is five (or three) dimensional 116. In any case, the states have to be diabatized before the golden rule expression or more advanced methods for computing rates of radiationless transitions can be employed.…”

Section: Intersystem Crossing Ratesmentioning

confidence: 99%

Spin–orbit coupling and intersystem crossing in molecules

Marian

2011

WIREs Comput Mol Sci

724

799

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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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Section: Intersystem Crossing Ratesmentioning

confidence: 99%

Spin–orbit coupling and intersystem crossing in molecules

Marian

2011

WIREs Comput Mol Sci

724

799

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“…The above description can be extended beyond two states, to describe degeneracies between three electronic states. − In that case, there are five conditions that need to be satisfied to reach degeneracy, and the branching space is five-dimensional. Three-state CoIns have been proven to be important in a variety of molecular systems. ,− …”

Section: Conical Intersectionsmentioning

confidence: 99%

Electronic Structure Methods for the Description of Nonadiabatic Effects and Conical Intersections

Matsika

2021

Chem. Rev.

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Nonadiabatic effects are ubiquitous in photophysics and photochemistry, and therefore, many theoretical developments have been made to properly describe them. Conical intersections are central in nonadiabatic processes, as they promote efficient and ultrafast nonadiabatic transitions between electronic states. A proper theoretical description requires developments in electronic structure and specifically in methods that describe conical intersections between states and nonadiabatic coupling terms. This review focuses on the electronic structure aspects of nonadiabatic processes. We discuss the requirements of electronic structure methods to describe conical intersections and nonadiabatic couplings, how the most common excited state methods perform in describing these effects, and what the recent developments are in expanding the methodology and implementing nonadiabatic couplings.

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“…SOC is intimately connected to the JT effects. 23,27,28,29,30,31,32,33,34,35,36,37,38,39,40 They are both related to degeneracy of electronic states. As we will see later, the SOC operator involves a dot product of electronic orbital angular momentum operator and electronic spin operator.…”

Section: Section 16 Spin-orbit Couplingmentioning

confidence: 99%