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Description of Conical Intersections with Density Functional Methods

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Density-Functional Methods for Excited States

Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 368))

Abstract

Conical intersections are perhaps the most significant mechanistic features of chemical reactions occurring through excited states. By providing funnels for efficient non-adiabatic population transfer, conical intersections govern the branching ratio of products of such reactions, similar to what the transition states do for ground-state reactivity. In this regard, intersections between the ground and the lowest excited states play a special role, and the correct description of the potential energy surfaces in their vicinity is crucial for understanding the mechanism and dynamics of excited-state reactions. The methods of density functional theory, such as time-dependent density functional theory, are widely used to describe the excited states of large molecules. However, are these methods suitable for describing the conical intersections or do they lead to artifacts and, consequently, to erroneous description of reaction dynamics? Here we address the first part of this question and analyze the ability of several density functional approaches, including the linear-response time-dependent approach as well as the spin-flip and ensemble formalisms, to provide the correct description of conical intersections and the potential energy surfaces in their vicinity. It is demonstrated that the commonly used linear-response time-dependent theory does not yield a proper description of these features and that one should instead use alternative computational approaches.

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Notes

  1. 1.

    See the chapter “Surface Hopping Dynamics with DFT Excited States” by M. Barbatti and R. Crespo-Otero.

  2. 2.

    As shown by Yarkony [74, 75], a rotation of the crossing states which orthogonalizes the BP vectors brings the vectors to a unique orientation, especially when symmetry is present. Application of such a prescription, however, modifies the BP vectors, while leaving the BP unchanged.

  3. 3.

    See also the chapter “Ensemble DFT approach to excited states of strongly correlated molecular systems” by M. Filatov.

  4. 4.

    See the chapter “Current status and recent developments in linear response time-dependent density-functional theory” by Mark E. Casida and Miquel Huix-Rotllant.

  5. 5.

    The conventional KS DFT/LR-TD-DFT calculations experienced severe convergence problems in the vicinity of the MECI point, which are reflected in the shape of the S 1 PES in the upper right panel of Fig. 5.

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Authors and Affiliations

  1. Institute of Physical and Theoretical Chemistry, Goethe University Frankfurt, Max-von-Laue-Str. 7, 60438, Frankfurt am Main, Germany

    Miquel Huix-Rotllant

  2. Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470, Mülheim an der Ruhr, Germany

    Alexander Nikiforov & Walter Thiel

  3. Institut für Physikalische und Theoretische Chemie, Universität Bonn, Beringstr. 4, 53115, Bonn, Germany

    Michael Filatov

Authors
  1. Miquel Huix-Rotllant
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  2. Alexander Nikiforov
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  3. Walter Thiel
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  4. Michael Filatov
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Correspondence to Michael Filatov .

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Editors and Affiliations

  1. Institut de Chimie Radicalaire, Université d'Aix-Marseille, Marseille, France

    Nicolas Ferré

  2. Inst. für Physikalische und Theoretische Chemie, Universität Bonn, Bonn, Germany

    Michael Filatov

  3. Institut für Physikalische und Theoretische Chemie, Goethe-Universität Frankfurt am Main, Frankfurt, Germany

    Miquel Huix-Rotllant

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Huix-Rotllant, M., Nikiforov, A., Thiel, W., Filatov, M. (2015). Description of Conical Intersections with Density Functional Methods. In: Ferré, N., Filatov, M., Huix-Rotllant, M. (eds) Density-Functional Methods for Excited States. Topics in Current Chemistry, vol 368. Springer, Cham. https://doi.org/10.1007/128_2015_631

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