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Related Experiment Videos

Can coupled-cluster theory treat conical intersections?

Andreas Köhn1, Attila Tajti

  • 1Institut für Physikalische Chemie, Universität Mainz, D-55099 Mainz, Germany. andreas.koehn@uni-mainz.de

The Journal of Chemical Physics
|August 4, 2007
PubMed
Summary
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Conical intersections are crucial for understanding ultrafast relaxation. This study addresses artifacts in coupled-cluster theory calculations of these intersections, offering a method to extract meaningful potential energy surfaces.

Area of Science:

  • Quantum Chemistry
  • Theoretical Chemistry
  • Molecular Dynamics

Background:

  • Conical intersections govern radiationless relaxation in molecules.
  • Accidental degeneracies are vital in larger molecular systems.
  • Coupled-cluster theory provides size-extensive electronic wave function descriptions.

Purpose of the Study:

  • To investigate artifacts arising from anti-Hermitian contributions in coupled-cluster theory near conical intersections.
  • To analyze the impact of these artifacts on near-degenerate electronic states.
  • To develop a method for extracting reliable potential energy surfaces.

Main Methods:

  • Equation-of-motion coupled-cluster (EOM-CC) calculations.
  • Analysis of linear dependent eigenvectors and complex eigenvalues.

Related Experiment Videos

  • Examination of anti-Hermitian contributions to coupling matrix elements.

    • Main Results:

    • Coupled-cluster theory, while size-extensive, loses its Hermitian character.
    • Numerical examples reveal artifacts in EOM-CC calculations of conical intersections.
    • These artifacts manifest as ill-behaved potential energy surfaces.

    Conclusions:

    • A simple method is proposed to extract physically meaningful potential energy surfaces.
    • This approach enables reliable calculations near conical intersections using coupled-cluster methods.
    • Provides a pathway for accurate modeling of ultrafast relaxation processes.