Ground-to-excited derivative couplings for the density functional-based tight-binding method: semi-local and long-range corrected formulations
| Autor: | Thomas A. Niehaus |
|---|---|
| Přispěvatelé: | Modélisation de la matière condensée et des interfaces (MMCI), Institut Lumière Matière [Villeurbanne] (ILM), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon |
| Jazyk: | angličtina |
| Rok vydání: | 2021 |
| Předmět: |
Physics
Coupling [PHYS]Physics [physics] Full density 010304 chemical physics Non-adiabatic coupling TD-DFTB Scalar (physics) LC-DFTB Conical surface 010402 general chemistry 01 natural sciences 0104 chemical sciences Range (mathematics) [SPI]Engineering Sciences [physics] Tight binding Excited state Quantum mechanics 0103 physical sciences Furan [CHIM]Chemical Sciences Physical and Theoretical Chemistry Functional theory |
| Zdroj: | Theoretical Chemistry Accounts: Theory, Computation, and Modeling Theoretical Chemistry Accounts: Theory, Computation, and Modeling, Springer Verlag, 2021, 140 (4), pp.34. ⟨10.1007/s00214-021-02735-y⟩ |
| ISSN: | 1432-881X 1432-2234 |
| DOI: | 10.1007/s00214-021-02735-y⟩ |
| Popis: | International audience; A derivation of non-adiabatic coupling vectors for the density functional-based tight-binding method (DFTB) between ground and excited states is presented. The analytical result is valid both for semi-local and long-range corrected DFTB and includes all required Pulay terms. Electron-translation factors lead to a conceptual simplification of the Slater-Koster scheme for precomputed integrals. Compared to scalar couplings obtained from numerical derivatives, the present approach is computationally more efficient and can be applied to systems with hundreds of atoms. The accuracy of DFTB derivative couplings is assessed by comparison to full density functional theory (DFT) calculations using semi-local and hybrid exchange-correlation functionals with promising results. As exemplified by a case study of furan, DFTB provides non-adiabatic coupling vectors that are close to DFT counterparts in size and direction also in the vicinity of conical intersections. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|
Full text from SpringerLink