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Related Experiment Video

Updated: Dec 8, 2025

Determination of the Excitation and Coupling Rates Between Light Emitters and Surface Plasmon Polaritons
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Dynamical correction to the Bethe-Salpeter equation beyond the plasmon-pole approximation.

Pierre-François Loos1, Xavier Blase2

  • 1Laboratoire de Chimie et Physique Quantiques (UMR 5626), Université de Toulouse, CNRS, UPS, Toulouse, France.

The Journal of Chemical Physics
|September 23, 2020
PubMed
Summary

This study introduces a new method to improve calculations of molecular optical excitation energies by including dynamical screening effects. This enhances accuracy beyond the static approximation in Bethe-Salpeter equation (BSE) calculations.

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Area of Science:

  • Computational chemistry
  • Quantum mechanics
  • Spectroscopy

Background:

  • The Bethe-Salpeter equation (BSE) formalism offers an affordable route to calculate accurate optical excitation energies.
  • Current BSE implementations often rely on a static approximation, limiting accuracy by neglecting frequency-dependent electron-hole screening.

Purpose of the Study:

  • To develop and implement a method that incorporates the dynamical correction of electron-hole screening into BSE calculations.
  • To improve the accuracy of calculated molecular excitation energies by going beyond the static approximation.

Main Methods:

  • A renormalized first-order perturbative correction was applied to static BSE excitation energies.
  • Dynamical screening of the Coulomb interaction was computed exactly within the random-phase approximation, surpassing the plasmon-pole approximation.
  • Calculations were benchmarked against high-level coupled-cluster methods.

Main Results:

  • The developed method successfully computes the dynamical correction for molecular excitation energies.
  • The inclusion of dynamical screening led to a clear improvement in the accuracy of calculated optical transitions.
  • Both singlet and triplet optical transitions showed enhanced accuracy.

Conclusions:

  • The proposed dynamical correction significantly improves the accuracy of Bethe-Salpeter equation calculations for optical excitation energies.
  • This approach provides a more rigorous treatment of electron-hole screening compared to the static approximation.
  • The method offers a valuable advancement for theoretical spectroscopy and computational materials science.