Hybrid Functional DFTB Parametrizations for Modeling Organic Photovoltaic Systems DOI Creative Commons
Wenbo Sun, Tammo van der Heide, Van Quan Vuong

и другие.

Journal of Chemical Theory and Computation, Год журнала: 2025, Номер unknown

Опубликована: Май 8, 2025

Density functional tight binding (DFTB) is a quantum chemical simulation method based on an approximate density theory (DFT), known for its low computational cost and comparable accuracy to DFT. For several years, the application of DFTB in organic photovoltaics (OPV) has been limited by absence appropriate set parameters that adequately account relevant elements necessary corrections. Here we have developed new parametrizations using hybrid functionals, including B3LYP CAM-B3LYP, OPV applications within order overcome self-interaction error present DFT functionals lacking long-range correction. These encompass electronic repulsive H, C, N, O, F, S, Cl. A Bayesian optimization approach was employed optimize free atom eigenenergies unoccupied shells. The effectiveness these evaluated data 12 donor acceptor molecules, showing consistent performance when compared with their corresponding references. Frontier molecular orbitals optimized geometries were examined evaluate predicting ground-state properties. Furthermore, excited-state properties monomers dimers investigated means real-time time-dependent (real-time TD-DFTB). appearance charge-transfer (CT) excitations observed, influence alkyl side-chains photoinduced CT process explored. This work paves way studying ground- properties, band alignments mechanisms at donor-acceptor interfaces, realistic systems.

Язык: Английский

Solvent Effects on Nonadiabatic Dynamics: Ab Initio Multiple Spawning Propagated on CASPT2/xTB Potentials DOI
Davide Avagliano

Journal of Chemical Theory and Computation, Год журнала: 2025, Номер unknown

Опубликована: Фев. 11, 2025

An approach to simulate nonadiabatic dynamics in solution is introduced, which relies on the propagation of nuclear wavepacket with Ab Initio Multiple Spawning (AIMS) method under effect potential energy calculated a hybrid but fully quantum mechanical scheme (QM/QM′). The electronic energies excited states chromophore are multireference perturbation theory (CASPT2), and embedding molecules described tight binding Hamiltonian (GFN2-xTB). This implementation open source combination PySpawn, OpenMolcas, xTB. Additionally, ORCA used properly generate initial conditions solution, showing how cutting-edge implementations several commonly software can push state art toward new high standard accuracy. ethylene vacuum, acetone, chloroform reported as test case, detailed analysis AIMS runs that shows important geometrical effects solvents decay mechanism chromophore.

Язык: Английский

Процитировано

0
Hybrid Functional DFTB Parametrizations for Modeling Organic Photovoltaic Systems DOI Creative Commons
Wenbo Sun, Tammo van der Heide, Van Quan Vuong

и другие.

Journal of Chemical Theory and Computation, Год журнала: 2025, Номер unknown

Опубликована: Май 8, 2025

Density functional tight binding (DFTB) is a quantum chemical simulation method based on an approximate density theory (DFT), known for its low computational cost and comparable accuracy to DFT. For several years, the application of DFTB in organic photovoltaics (OPV) has been limited by absence appropriate set parameters that adequately account relevant elements necessary corrections. Here we have developed new parametrizations using hybrid functionals, including B3LYP CAM-B3LYP, OPV applications within order overcome self-interaction error present DFT functionals lacking long-range correction. These encompass electronic repulsive H, C, N, O, F, S, Cl. A Bayesian optimization approach was employed optimize free atom eigenenergies unoccupied shells. The effectiveness these evaluated data 12 donor acceptor molecules, showing consistent performance when compared with their corresponding references. Frontier molecular orbitals optimized geometries were examined evaluate predicting ground-state properties. Furthermore, excited-state properties monomers dimers investigated means real-time time-dependent (real-time TD-DFTB). appearance charge-transfer (CT) excitations observed, influence alkyl side-chains photoinduced CT process explored. This work paves way studying ground- properties, band alignments mechanisms at donor-acceptor interfaces, realistic systems.

Язык: Английский

Процитировано

0