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Marek, Štěpán ; Wilhelm, Jan

Linear and Nonlinear Optical Properties of Molecules from Real-Time Propagation Based on the Bethe–Salpeter Equation

Marek, Štěpán and Wilhelm, Jan (2025) Linear and Nonlinear Optical Properties of Molecules from Real-Time Propagation Based on the Bethe–Salpeter Equation. Journal of Chemical Theory and Computation 21 (19), pp. 9814-9822.

Date of publication of this fulltext: 15 Oct 2025 13:23
Article
DOI to cite this document: 10.5283/epub.77967


Abstract

We present a real-time propagation method for computing linear and nonlinear optical properties of molecules based on the Bethe–Salpeter equation. The method follows the time evolution of the one-particle density matrix under an external electric field. We include electron–electron interaction effects through a self-energy model based on the screened exchange approximation. Quasiparticle energies ...

We present a real-time propagation method for computing linear and nonlinear optical properties of molecules based on the Bethe–Salpeter equation. The method follows the time evolution of the one-particle density matrix under an external electric field. We include electron–electron interaction effects through a self-energy model based on the screened exchange approximation. Quasiparticle energies are taken from a prior GW calculation to construct the effective single-particle Hamiltonian, and we represent all operators and wave functions in an atom-centered Gaussian basis. We benchmark the accuracy of the real-time propagation against the standard linear-response Bethe–Salpeter equation by using a set of organic molecules. We find very good agreement when computing linear-response isotropic polarizability spectra from both approaches with a mean absolute deviation of 30 meV in peak positions. Beyond linear response, we simulate second harmonic generation and optical rectification in a noncentrosymmetric molecule. We foresee broad applicability of real-time propagation based on the Bethe–Salpeter equation for the study of linear and nonlinear optical properties of molecules, as the method has a computational cost similar to that of time-dependent density functional theory with hybrid functionals.



Involved Institutions


Details

Item typeArticle
Journal or Publication TitleJournal of Chemical Theory and Computation
Publisher:American Chemical Society (ACS)
Open Access Type:ACS Hybrid
Volume:21
Number of Issue or Book Chapter:19
Page Range:pp. 9814-9822
Date25 September 2025
InstitutionsPhysics > Institute of Theroretical Physics
Regensburg Center for UltrafastNanoscopy (RUN)
Projects
Funded by: Deutsche Forschungsgemeinschaft (DFG) (503985532)
Funded by: Deutsche Forschungsgemeinschaft (DFG) (314695032)
Funded by: Deutsche Forschungsgemeinschaft (DFG) (5394206)
Funded by: Deutsche Forschungsgemeinschaft (DFG) (UNSPECIFIED)
Identification Number
ValueType
10.1021/acs.jctc.5c01246DOI
arXiv:2507.21279arXiv ID
Keywordsoptical properties, real-time propagation, Bethe-Salpeter equation, DFT, laser pulse
Dewey Decimal Classification500 Science > 530 Physics
500 Science > 540 Chemistry & allied sciences
StatusPublished
RefereedYes, this version has been refereed
Created at the University of RegensburgYes
URN of the UB Regensburgurn:nbn:de:bvb:355-epub-779678
Item ID77967

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