Nonadiabatic Dynamics Simulations for Photoinduced Processes in Molecules and Semiconductors: Methodologies and Applications

Liu, Xiang-Yang; Chen, Wen-Kai; Fang, Wei-Hai; Cui, Ganglong

doi:10.1021/acs.jctc.3c00960

Cited by 9 publications

(1 citation statement)

References 404 publications

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“…Nonadiabatic electron–phonon coupling facilitates charge carrier transitions, playing a crucial role in technologies such as solar cells, , quantum information systems, , and spintronic devices. − Typically, nonadiabatic coupling (NAC) is computed at a single k -point in momentum space, which constrains nonadiabatic molecular dynamics (NA-MD) to only manage vertical transitions of charge carriers. , This limitation prevents the NA-MD from addressing nonvertical transitions among multiple k-points, which requires additional nonzero phonons to conserve the momentum of electrons during electronic transitions. On the basis of the harmonic approximation and using the electron–phonon coupling, the nonvertical transitions can be handled by the real-time Boltzmann transport equation − or surface hopping based quantum dynamics .…”

Section: Introductionmentioning

confidence: 99%

Nonadiabatic Molecular Dynamics in Momentum Space Beyond Harmonic Approximation: Hot Electron Relaxation in Photoexcited Black Phosphorus

Lu,

Fang,

Long

2024

J. Am. Chem. Soc.

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We simulated hot-electron relaxation in black phosphorus using the nonadiabatic molecular dynamics (NA-MD) approach with a non-Condon effect in momentum space beyond the harmonic approximation. By comparing simulations at the Γ point in a large supercell with those using a few k-points in a smaller supercell�while maintaining the same number of electronic states within the same energy range, we demonstrate that both setups yield remarkably consistent energy relaxation times, regardless of the initial state energy. This consistency arises from the complementary effects of supercell size in real space and the number of k-points in the reciprocal space. This finding confirms that simulations at a single k-point in large size supercells are an effective approximation for NA-MD with a non-Condon effect. This approach offers significant advantages for complex photophysics, such as intervalley scattering and indirect bandgap charge recombination, and is particularly suitable for large systems without the need for a harmonic approximation.

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Section: Introductionmentioning

confidence: 99%

Nonadiabatic Molecular Dynamics in Momentum Space Beyond Harmonic Approximation: Hot Electron Relaxation in Photoexcited Black Phosphorus

Lu,

Fang,

Long

2024

J. Am. Chem. Soc.

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Conformational and Solvent Effects on the Photoinduced Electron Transfer Dynamics of a Zinc Phthalocyanine–Benzoperylenetriimide Conjugate: A Nonadiabatic Dynamics Simulation

Liu,

Wei,

Zheng

et al. 2024

ChemPhysChem

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Herein, we employed a combination of static electronic structure calculations and nonadiabatic dynamics simulations at linear‐response time dependent density functional theory (LR‐TDDFT) level with the optimally tuned range‐separated hybrid (OT‐RSH) functional to explore the ultrafast photoinduced dynamics of a zinc phthalocyanine‐benzoperylenetriimide (ZnPc‐BPTI) conjugate. Due to the flexibility of the linker, we identified two major conformations: the stacked conformation (ZnPc‐BPTI‐1) and the extended conformation (ZnPc‐BPTI‐2). Since the charge transfer states are much lower than the lowest local excitation in ZnPc‐BPTI‐1, which is contrary to ZnPc‐BPTI‐2, the ultrafast electron transfer (~3.6 ps) is only observed in the nonadiabatic simulations of ZnPc‐BPTI‐1 upon local excitation around the absorption maximum of ZnPc. However, when considering the solvent effects in benzonitrile: the lowest S1 states are both charge transfer states from ZnPc to BPTI for different conformers. Subsequent nonadiabatic dynamics simulations indicate that both conformers experience ultrafast electron transfer in benzonitrile with two time constants of 90 [100] fs and 1.40 [1.43] ps. Our present work not only agrees well with previous experimental study, but also points out the important role of conformational changes and solvent effects in regulating the photodynamics of organic donor‐acceptor conjugates.

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Phenol Photostatic Spectra and Quantum‐Classical Photodynamic Deprotonation

Pomogaev,

Bocharnikova,

Tchaikovskaya

et al. 2024

Int J of Quantum Chemistry

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The spectral‐luminescence properties and photochemical conversions of phenol were analyzed for an isolated molecule as well as in water solvents in a continuum implicit model and explicit atomistic surroundings. This involved employing cut‐edge hybrid quantum‐classical methodologies to generate static optical spectra and the excited dissipative crossing potential energy curves. A combination of electronic excitations, gradient calculations, and embedding electrostatic potential fitting charges on quantum‐classical molecular dynamic propagation trajectories provided statistically averaged absorption spectra. The mixed‐reference spin‐flip multiconfigurational linear response method based on reference triplet preprocessed in the time‐dependent density‐functional theory was utilized to determine conical intersections between the lowest excited and ground states, as well as two‐stage transitions from the second excitation to the ground state. Non‐adiabatic quantum‐classical molecular dynamics defined photodissipative trajectories of excited states, their lifetimes, and crossing points through trajectory surface hopping together with the mixed‐reference spin‐flip and embedding electrostatic potential fitting approaches. Dyson orbitals of the extended Koopmans' theorem were applied to reveal the nature of molecular states at conical intersections and key points on photodynamic trajectories. Potential hydroxyl group cleavage predicted with conical intersections searching turns to “swift” OH deprotonation through |π→⟩ transition along photodynamic propagations in contrast with “long” processes leading to benzene ring deformation with stable OH bond.

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Nonadiabatic Dynamics Simulations for Photoinduced Processes in Molecules and Semiconductors: Methodologies and Applications

Cited by 9 publications

References 404 publications

Nonadiabatic Molecular Dynamics in Momentum Space Beyond Harmonic Approximation: Hot Electron Relaxation in Photoexcited Black Phosphorus

Nonadiabatic Molecular Dynamics in Momentum Space Beyond Harmonic Approximation: Hot Electron Relaxation in Photoexcited Black Phosphorus

Conformational and Solvent Effects on the Photoinduced Electron Transfer Dynamics of a Zinc Phthalocyanine–Benzoperylenetriimide Conjugate: A Nonadiabatic Dynamics Simulation

Phenol Photostatic Spectra and Quantum‐Classical Photodynamic Deprotonation

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