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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

Artikel

Marek, Štěpán und 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), S. 9814-9822.

DOI zum Zitieren dieses Dokuments: 10.5283/epub.77967


Zusammenfassung

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.



Beteiligte Einrichtungen


Details

DokumentenartArtikel
Titel eines Journals oder einer ZeitschriftJournal of Chemical Theory and Computation
VerlagAmerican Chemical Society (ACS)
Open Access ArtACS Hybrid
Band21
Nummer des Zeitschriftenheftes oder des Kapitels19
SeitenbereichS. 9814-9822
Datum25 September 2025
Veröffentlichungsdatum15 Okt 2025 13:23
InstitutionenPhysik > Institut für Theoretische Physik
Regensburg Center for Ultrafast Nanoscopy (RUN)
Projekte
Gefördert von: Deutsche Forschungsgemeinschaft (DFG) (503985532)
Gefördert von: Deutsche Forschungsgemeinschaft (DFG) (314695032)
Gefördert von: Deutsche Forschungsgemeinschaft (DFG) (5394206)
Gefördert von: Deutsche Forschungsgemeinschaft (DFG) (Nicht ausgewählt)
Identifikationsnummer
WertTyp
10.1021/acs.jctc.5c01246DOI
arXiv:2507.21279arXiv-ID
Stichwörter / Keywordsoptical properties, real-time propagation, Bethe-Salpeter equation, DFT, laser pulse
Dewey-Dezimal-Klassifikation500 Naturwissenschaften und Mathematik > 530 Physik
500 Naturwissenschaften und Mathematik > 540 Chemie
StatusVeröffentlicht
BegutachtetJa, diese Version wurde begutachtet
An der Universität Regensburg entstandenJa
URN der UB Regensburgurn:nbn:de:bvb:355-epub-779678
Dokumenten-ID77967

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