Photoinduced charge-transfer in chromophore-labeled gold nanoclusters: quantum evidence of the critical role of ligands and vibronic couplings

Domínguez-Castro, Adrian; Lien-Medrano, Carlos R.; Maghrebi, Khaoula; Messaoudi, Sabri; Frauenheim, Thomas; Fihey, Arnaud

doi:10.1039/d1nr00213a

Cited by 13 publications

(15 citation statements)

References 55 publications

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“…At time t 0 a Dirac-delta type electric field pulse perturbation E → normal k i c k ( t ) = E 0 δ( t – t 0 ) ê is imposed to the density matrix ρ̂ at the ground state, where the E 0 is the field strength and ê is the direction. After that, the density matrix ρ̂ evolves in time and it can be calculated by the Liouville–von Neumann equation of motion: , i ℏ ∂ ρ̂ ∂ t = Ŝ − 1 Ĥ ρ̂ − ρ̂ Ĥ Ŝ − 1 where Ŝ is the overlap matrix and Ĥ is the system Hamiltonian including the external field.…”

Section: Methodsmentioning

confidence: 99%

“…This classical field approximation has been successfully adopted for study of photoexcitation processes of more complex systems . More recently, this classical approximation has been widely used in a variety of cases, such as transient light absorption of organic molecules, the charge transfer in a nanodiamond donor–acceptor complex, , chromophore-labeled gold nanoclusters, , dye-TiO 2 and molecular aggregates, and the impulsive vibrational spectroscopy in DNA/RAN nucleobases . All of them emphasize the importance of taking account of nucleus motion when describing charge transfer processes with photoexcitation, which can be investigated with classical electric field approximation.…”

Section: Introductionmentioning

confidence: 99%

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Photoinduced Charge Behavior in a-Si:H/c-Si Heterojunction: Quantum Dynamics Simulation with Vibronic Coupling

Matsumoto

2023

J. Phys. Chem. C

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Excellent charge carrier behavior in hydrogenated amorphous silicon/crystalline silicon (a-Si:H/c-Si) is crucial for achieving the high efficiency and stability of Si heterojunction solar cells. In this work, we employ the real-time time-dependent density functional based tight binding (TD-DFTB) approach with the Ehrenfest dynamic method to investigate how vibronic coupling affects the photoinduced charge behavior in a-Si:H/c-Si. The variation in hydrogen concentration demonstrates the diversity of intermaterial charge transfer. The hydrogen directly leads to structural differences and thus indirectly affects charge separation and transfer, emphasizing the importance of hydrogen in the charge transfer process. Doping c-Si with aluminum or phosphorus improves the intermaterial charge separation transfer and, to some extent, suppresses charge carrier recombination. Furthermore, lattice vibration mode analysis shows that, while a-Si:H primarily contributes to defect passivation and carrier-selective transporting, the charge separation and transfer are also significantly affected. The intense phonon vibration modes indicate the presence of a nonradiative recombination mechanism, which results in the gradual energy fading.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Photoinduced Charge Behavior in a-Si:H/c-Si Heterojunction: Quantum Dynamics Simulation with Vibronic Coupling

Matsumoto

2023

J. Phys. Chem. C

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“…In order to get the photoabsorption spectrum over the full UV/vis region, more viable alternatives are thus developing around semiempirical approaches. The pristine tight-binding variant to LR-TDDFT (TD-DFTB) is one of them. , Efforts are currently dedicated to its application to standard and more complex architectures such as dimer assemblies of noble metal nanorods. − However, being prone to self-interaction and delocalization errors (SIE and DE, respectively) just like DFT in its semilocal exchange-correlation approximation, , the approach strongly underestimates charge-transfer-like excitations. Since the latter strongly govern the absorption spectra of such extended and electronically delocalized system, “ghost excitations” have to be carefully identified prior interpretations …”

Section: Introductionmentioning

confidence: 99%

Modeling the Photo-Absorption Properties of Noble Metal Nanoclusters: A Challenge for Density-Functional Theory

et al. 2023

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Modeling the emergence of the plasmon resonance in noble metal nanoclusters is still a challenge to overcome for theoretical chemistry. The systems are indeed too small to neglect quantum-size effects but too large to be easily addressed with quantum mechanics. We test here a robust answer to this still open question: the simplified variant to time-dependent density-functional theory (TDDFT). Applied to extended systems, this electronic structure-based method succeeds in computing a sufficient number of excitations to cover the emergence of plasmon-like states. By employing it under a semilocal exchange-correlation approximation such as PBE, we show that the most intense absorption band, which could be wrongly assigned to the plasmon band, has a strong interband character. We suspect the too low energy gap between (n–1)d and ns valence orbitals as the origin of the d-contamination of the excitations. We demonstrate however that a global or range-separated hybrid exchange-correlation approximation such as PBE0 or RSX-PBE0 is a robust answer to the problem. We notice that both approximations are not able to solve at the same time the energy positioning and intensity of the plasmon band, PBE0 being more accurate for energy positioning and RSX-PBE0 for intensity. All in all, we warn the user that a random choice of the exchange-correlation approximation opens the door to getting the correct answer for the wrong reason.

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“…42,43 Efforts are currently dedicated to its application to standard and more complex architectures such as dimer assemblies of noble metal nanorods. [44][45][46][47][48] However, being prone to self-interaction and delocalization errors (SIE and DE, respectively) just like DFT in its semilocal exchange-correlation approximation, 49,50 the approach strongly underestimates charge-transfer-like excitations. Since the latter strongly govern the absorption spectra of such extended and electronically delocalized system, 'ghost excitations' have to be carefully identified prior interpretations.…”

Section: Introductionmentioning

confidence: 99%

Modeling the Photo-Absorption Properties of Noble Metal Nanoclusters: a Challenge for Density-Functional Theory

SEVEUR

Boubekeur-Lecaque

Maurel

et al. 2023

Preprint

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Modeling the emergence of the plasmon resonance in noble metal nanoclusters is still a challenge to overcome for theoretical chemistry. The systems are indeed too small to neglect quantum-size effects but too large to be easily addressed with quantum mechanics. We test here a robust answer to this still open question: the simplified variant to time-dependent density-functional theory (TDDFT). Applied to extended systems, this electronic structure-based method succeeds to compute a sufficient number of excitations to cover the emergence of plasmon-like states. By employing it under a semilocal exchange-correlation approximation such as PBE, we show that the most intense absorption band, that could be wrongly assigned to the plasmon band, has a strong interband character. We suspect the too low energy gap between $(n-1)d$ and $ns$ valence orbitals as the origin of the $d$-contamination of the excitations. We demonstrate however that a global or range-separated hybrid exchange-correlation approximation such as PBE0 or RSX-PBE0 is a robust answer to the problem. We notice that both approximations are not able to solve at the same time the energy positioning and intensity of the plasmon band, PBE0 being more accurate for energy positioning and RSX-PBE0 for intensity. All in all, we warn the user that a random choice of the exchange-correlation approximation opens the door to getting the correct answer for the wrong reason.

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Photoinduced charge-transfer in chromophore-labeled gold nanoclusters: quantum evidence of the critical role of ligands and vibronic couplings

Abstract: The electron flow between a metallic aggregate and an organic molecule after excitation with light is a crucial step on which are based the hybrid photovoltaic nanomaterials. So far, designing...

Cited by 13 publications

References 55 publications

Photoinduced Charge Behavior in a-Si:H/c-Si Heterojunction: Quantum Dynamics Simulation with Vibronic Coupling

Photoinduced Charge Behavior in a-Si:H/c-Si Heterojunction: Quantum Dynamics Simulation with Vibronic Coupling

Modeling the Photo-Absorption Properties of Noble Metal Nanoclusters: A Challenge for Density-Functional Theory

Modeling the Photo-Absorption Properties of Noble Metal Nanoclusters: a Challenge for Density-Functional Theory

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