Vibronic Couplings and Temperature Effects in the Ultrafast Dynamics of a Charge-Transfer Complex DOI Creative Commons
Matheus Jacobs, Jannis Krumland, Ana M. Valencia

и другие.

arXiv (Cornell University), Год журнала: 2023, Номер unknown

Опубликована: Янв. 1, 2023

The ultrafast dynamics of charge carriers in organic donor-acceptor interfaces are primary importance to understanding the fundamental properties these systems. In this work, we focus on a charge-transfer complex formed by quaterthiophene $p$-doped tetrafluoro-tetracyanoquinodimethane and investigate electron vibronic interactions also at finite temperatures applying femtosecond pulse resonance with two lowest-energy excitations system perpendicular parallel polarization respect interface. adopted \textit{ab initio} formalism based real-time time-dependent density-functional theory coupled Ehrenfest enables monitoring dynamical transfer across interface assessing role played nuclear motion. Our results show that strong intermolecular binding already ground state influence dynamics, too. analysis motion involved processes reveals participation different vibrational modes depending electronic states stimulated resonant pulse. Coupled mostly excited polarized interface, while intramolecular vibrations donor molecule dominate excitation orthogonal direction. obtained overall consistent picture, although thermal disorder contributes slightly decreasing interfacial transfer.

Язык: Английский

A multi-state mapping approach to surface hopping DOI Creative Commons
Johan E. Runeson, David E. Manolopoulos

The Journal of Chemical Physics, Год журнала: 2023, Номер 159(9)

Опубликована: Сен. 7, 2023

We describe a multiple electronic state adaptation of the mapping approach to surface hopping introduced recently by Mannouch and Richardson [J. Chem. Phys. 158, 104111 (2023)]. Our modification treats populations coherences on an equal footing is guaranteed give in any basis that tend correct quantum–classical equilibrium values long-time limit (assuming ergodicity). demonstrate its accuracy comparison with exact benchmark results for three- seven-state models Fenna–Matthews–Olson complex, obtaining are significantly more accurate than those fewest switches at least as good other semiclassical method we aware of. Since these were obtained adapting scheme Richardson, go compare our theirs variety problems two states. find their sometimes accurate, especially Marcus inverted regime. However, situations, accuracies comparable, since can be used states it applied wider electronically nonadiabatic systems.

Язык: Английский

Процитировано

36
Surface hopping modeling of charge and energy transfer in active environments DOI Creative Commons
Josene M. Toldo, Mariana T. do Casal, Elizete Ventura

и другие.

Physical Chemistry Chemical Physics, Год журнала: 2023, Номер 25(12), С. 8293 - 8316

Опубликована: Янв. 1, 2023

An active environment changes the photophysics of an excited chromophore. Surface hopping simulations are crucial to understanding how.

Язык: Английский

Процитировано

21
Modeling Excited States of Molecular Organic Aggregates for Optoelectronics DOI Creative Commons
Federico J. Hernández, Rachel Crespo‐Otero

Annual Review of Physical Chemistry, Год журнала: 2023, Номер 74(1), С. 547 - 571

Опубликована: Фев. 16, 2023

Light-driven phenomena in organic molecular aggregates underpin several mechanisms relevant to optoelectronic applications. Modeling these processes is essential for aiding the design of new materials and optimizing devices. In this review, we cover use different atomistic models, excited-state dynamics, transport approaches understanding light-activated aggregates, including radiative nonradiative decay pathways. We consider both intra- intermolecular focus on role conical intersections as facilitators internal conversion. explore exciton models Frenkel charge transfer states electronic structure methods algorithms commonly applied dynamics. Throughout analyze approximations employed simulation conversion, intersystem crossing, reverse crossing rates behind single fission, triplet-triplet annihilation, Dexter energy transfer, Förster transfer.

Язык: Английский

Процитировано

18
Delocalisation enables efficient charge generation in organic photovoltaics, even with little to no energetic offset DOI Creative Commons
Daniel Balzer, Ivan Kassal

Chemical Science, Год журнала: 2024, Номер 15(13), С. 4779 - 4789

Опубликована: Янв. 1, 2024

Organic photovoltaics (OPVs) are promising candidates for solar-energy conversion, with device efficiencies continuing to increase. However, the precise mechanism of how charges separate in OPVs is not well understood because low dielectric constants produce a strong attraction between charges, which they must overcome separate. Separation has been thought require energetic offsets at donor-acceptor interfaces, but recent materials have enabled efficient charge generation small offsets, or none all neat materials. Here, we extend delocalised kinetic Monte Carlo (dKMC) develop three-dimensional model that includes disorder, delocalisation, and polaron formation every step from photoexcitation separation. Our simulations show delocalisation dramatically increases charge-generation efficiency, partly by enabling excitons dissociate bulk. Therefore, can be even devices little no offset, including findings demonstrate underlying quantum-mechanical effect improves charge-separation kinetics faster longer-distance hops states, mediated hybridised states exciton charge-transfer character.

Язык: Английский

Процитировано

7
On the role of charge transfer excitations in non-fullerene acceptors for organic photovoltaics DOI Creative Commons
Samuele Giannini,

Daniel J. C. Sowood,

Jesús Cerdá

и другие.

Materials Today, Год журнала: 2024, Номер 80, С. 308 - 326

Опубликована: Сен. 24, 2024

Язык: Английский

Процитировано

7
ML-MCTDH-Aid: An auxiliary package for multilayer multiconfiguration time-dependent Hartree calculations DOI
Jie Zheng, Yu Xie, Jiawei Peng

и другие.

The Journal of Chemical Physics, Год журнала: 2025, Номер 162(5)

Опубликована: Фев. 4, 2025

The multilayer-multiconfiguration time-dependent Hartree (ML-MCTDH) method has garnered significant attention in the realm of theoretical chemistry owing to its powerful ability perform numerically exact descriptions multi-dimensional quantum dynamics and exhibit remarkable performance simulating nonadiabatic complex systems. Despite availability computational packages within ML-MCTDH framework, executing these calculations seamlessly is not a straightforward task. Typically, substantial efforts are necessitated configure correct inputs for calculations, which require correctly define several non-trivial parameters, reasonably setup optimal tree expansion wavefunctions, properly select basis function numbers. To address challenges, we have developed an auxiliary package named ML-MCTDH-Aid, facilitates using Heidelberg MCTDH user-friendly manner. This primarily tailored handle high-dimensional governed by Hamiltonian composed electronic states, vibrational modes their linear vibronic coupling terms. It automatically generates multiple essential input files, all can be performed all-in-one black-box easy-to-use show utility ML-MCTDH-Aid package, provide step-by-step tutorial that demonstrates running studies on three models. These examples illuminate how utilization significantly enhances efficiency effectiveness calculations. substantially boosts accessibility tackling

Язык: Английский

Процитировано

1
Dissecting the nature and dynamics of electronic excitations in a solid-state aggregate of a representative non-fullerene acceptor DOI Creative Commons
Samuele Giannini, Jesús Cerdá, Giacomo Prampolini

и другие.

Journal of Materials Chemistry C, Год журнала: 2024, Номер 12(27), С. 10009 - 10028

Опубликована: Янв. 1, 2024

Understanding electronic excitations and their dynamics in non-fullerene acceptors is crucial for enhancing opto-electronic properties. Using a Frenkel-exciton Hamiltonian non-adiabatic dynamics, we reveal design strategies to achieve this goal.

Язык: Английский

Процитировано

5
Disorder-Induced Transition from Transient Quantum Delocalization to Charge Carrier Hopping Conduction in a Nonfullerene Acceptor Material DOI Creative Commons
Ljiljana Stojanović, Jack F. Coker, Samuele Giannini

и другие.

Physical Review X, Год журнала: 2024, Номер 14(2)

Опубликована: Апрель 29, 2024

Nonfullerene acceptors have caused a step change in organic optoelectronics research but little is known about the mechanism and factors limiting charge transport these molecular materials. Here joint computational-experimental investigation presented to understand impact of various sources disorder on electron nonfullerene acceptor O-IDTBR. We find that single crystals this material, occurs transient quantum delocalization regime with excess delocalized over three molecules average, according quantum-classical nonadiabatic molecular-dynamics simulations. In regime, carrier mobility (μa=7 cm2 V−1 mathvariant="normal">s−1) are limited by dynamical off-diagonal diagonal electron-phonon coupling. assemblies representing disordered thin films, additional static coupling sufficient fully localize molecules, concomitant transition from small polaron hopping drop 1 order magnitude. Yet, inclusion resulting electrostatic interactions arising acceptor-donor-acceptor (A-D-A) structure O-IDTBR, found most dramatic mobility, further 4–5 orders magnitude 10−5 cm2 V−1 mathvariant="normal">s−1, good agreement thin-film estimated space-charge-limited-current measurements. Limitations due likely apply acceptors. They imply while A-D-A or A-DAD-A motifs beneficial for photoabsorption exciton transport, they create can limit optoelectronic applications. This work shows value computational methods, particular, propagation carriers, distinguish different regimes types packing. Published American Physical Society 2024

Язык: Английский

Процитировано

4
Excitonic Configuration Interaction: Going Beyond the Frenkel Exciton Model DOI Creative Commons
Tomislav Piteša, Severin Polonius, Leticia González

и другие.

Journal of Chemical Theory and Computation, Год журнала: 2024, Номер 20(13), С. 5609 - 5634

Опубликована: Июнь 17, 2024

We present the excitonic configuration interaction (ECI) method─a fragment-based analogue of CI method for electronic structure calculations multichromophoric systems. It can also be viewed as a generalization exciton approach, with following properties: (i) constructs effective Hamiltonian exclusively from monomer calculations. (ii) employs strong orthogonality assumption and is exact within McWeeny's group function theory, thus requiring only one-electron density matrices states. (iii) agnostic method, allowing us to use/combine different methods. (iv) includes an embedding point charge scheme (called Hartree–Fock, EHF) improve accuracy states, but such that full-system not explicitly dependent on embedding. (v) systematically improvable, by expanding set states including configurations where two or more monomers are excited (defining ECIS, ECISD, etc., methods). The performance ECI assessed computing absorption spectrum exemplary systems, using CIS method. significantly depends chosen charges expansion. most accurate combinations─ECIS ECISD EHF embedding─yield spectra agree qualitatively quantitatively direct calculations, deviations excitation energies below 0.1 eV. show based predict simultaneously (e.g., triplet–triplet double-local excitations) inaccessible in calculation.

Язык: Английский

Процитировано

4
Charge transport in organic semiconductors from the mapping approach to surface hopping DOI Creative Commons
Johan E. Runeson,

Thomas J. G. Drayton,

David E. Manolopoulos

и другие.

The Journal of Chemical Physics, Год журнала: 2024, Номер 161(14)

Опубликована: Окт. 8, 2024

We describe how to simulate charge diffusion in organic semiconductors using a recently introduced mixed quantum-classical method, the mapping approach surface hopping. In contrast standard fewest-switches hopping, this method propagates classical degrees of freedom deterministically on most populated adiabatic electronic state. This correctly preserves equilibrium distribution quantum coupled phonons, allowing one time-average along trajectories improve statistical convergence calculation. illustrate with an application model for transport direction maximum mobility crystalline rubrene. Because its consistency distribution, present gives time-dependent coefficient that plateaus long-time limiting value. The resulting is somewhat higher than relaxation time approximation, which uses phenomenological parameter obtain non-zero from calculation static phonon disorder. However, it very similar obtained Ehrenfest dynamics, at least regimes we have investigated here. surprising because dynamics overheats subsystem and is, therefore, inconsistent distribution.

Язык: Английский

Процитировано

3