JOYCE3.0: A General Protocol for the Specific Parametrization of Accurate Intramolecular Quantum Mechanically Derived Force Fields

Journal of Chemical Theory and Computation, Journal Year: 2025, Volume and Issue: unknown

Published: March 11, 2025

While the intrinsically multiscale nature of most advanced materials necessitates use cost-effective computational models based on classical physics, a reliable description structure and dynamics their components often requires quantum-mechanical treatment. In this work, we present JOYCE3.0, software package for parametrization accurate, quantum-mechanically derived force fields (QMD-FFs). Since its original release, code has been extensively automated expanded, with all novel implementations thoroughly discussed. To illustrate general applicability, QMD-FFs are parametrized seven benchmark cases, encompassing molecules diverse structures properties. These range from exotic stiff scaffolds, flexible polymeric chains, polyenes biological interest to transition-metal complexes. On one hand, JOYCE3.0 FFs consistently outperform available general-purpose descriptions, achieving excellent agreement higher-level theoretical methods or experimental validation data. other remarkable accuracy found in molecular extends electronic excited states, enabling integration into multilevel protocols aimed at reliably predicting selected properties spectral line shapes optoelectronic materials. The high quality results─spanning structures, condensed-phase properties, spectroscopic features─in combination enhanced interface popular codes engines, as well applicability chemically species, strongly suggests that could play pivotal role rational design functionalized heterogeneous systems.

Language: Английский

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On the role of charge transfer excitations in non-fullerene acceptors for organic photovoltaics

Materials Today, Journal Year: 2024, Volume and Issue: 80, P. 308 - 326

Published: Sept. 24, 2024

Language: Английский

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Dissecting the nature and dynamics of electronic excitations in a solid-state aggregate of a representative non-fullerene acceptor

Journal of Materials Chemistry C, Journal Year: 2024, Volume and Issue: 12(27), P. 10009 - 10028

Published: Jan. 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.

Language: Английский

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A Set of Quantum-Mechanically Derived Force Fields for Natural and Synthetic Retinal Photoswitches

Journal of Chemical Theory and Computation, Journal Year: 2025, Volume and Issue: unknown

Published: April 28, 2025

The diverse biological functions of rhodopsins are all triggered by the photoexcitation retinal protonated Schiff base chromophores. This diversity can be traced back not only to variations in protein scaffolds which chromophore is embedded, but also different isomeric forms itself, whose role crucial several processes. Although most computational approaches for these systems often require classical molecular dynamics, efforts providing a set parameters able accurately and consistently model chromophores lacking literature. recent entail either refinements general purpose force fields accuracy, or parametrization strategies that include environmental effects, makes resulting transferable embedding. In this work, we provide accurate intramolecular based on data purposely computed using Møller-Plesset second order perturbation theory, specifically tailored varied natural bases synthetic analogues employed retinal-based photoswitches. We demonstrate quality our quantum-mechanically derived (QMD-FFs) through wide validation tests. These indicate QMD-FFs outperform cases transferable, general-purpose FFs, delivering an excellent description each terms equilibrium geometries, conformational landscapes, optical properties comparison literature data, experimental measurements, reference QM calculations. Our QMD-FFs, distributed electronic format, adopted describe complex environments, exploiting intermolecular compatible with those available macromolecules.

Language: Английский

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Towards a fast machine-learning-assisted prediction of the mechanoelectric response in organic crystals

Journal of Materials Chemistry C, Journal Year: 2023, Volume and Issue: 11(36), P. 12297 - 12306

Published: Jan. 1, 2023

A protocol combining molecular dynamics, density functional theory, machine learning, and kinetic Monte Carlo accurately predicts the dependence of charge mobility on mechanical deformations for organic semiconductors.

Language: Английский

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Systematic computational research dealing with the effect of molecular size, heteroatom substitution and modification site on electronic properties, absorption and charge transfer ability of fused ring electron acceptors

Next Materials, Journal Year: 2024, Volume and Issue: 6, P. 100315 - 100315

Published: July 31, 2024

Language: Английский

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Fast Nonradiative Decay Paths in Organic Solar Cells: Implications for Designing More Efficient Photovoltaic Systems

ACS Applied Energy Materials, Journal Year: 2023, Volume and Issue: unknown

Published: Dec. 28, 2023

With the aim of understanding sources energy losses in bulk heterojunction solar cells, rates elementary charge-transfer processes occurring at donor–acceptor interface have been determined by employing a combined classical and quantum mechanical approach for four prototypical blends, covering wide range power conversion efficiency values. The results show that backward electron transfer from state D/A to ground is fast process, which can efficiently compete with charge dissociation; indeed, clear–cut correlation between nonradiative recombination observed has found. finding presented above suggests important criteria rational design acceptor–donor blends organic photovoltaics.

Language: Английский

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Genesis of the Chirality of Polythiophene Aggregates from Classical Molecular Dynamics

The Journal of Physical Chemistry C, Journal Year: 2024, Volume and Issue: 128(46), P. 19901 - 19911

Published: Nov. 7, 2024

Conjugated polymers are widely used in electronic devices whose performance is highly dependent on their properties. Properties and influenced by the supramolecular organization of chromophores constituting polymer backbone, identifying structure–property relationships crucial to design better devices. Polythiophenes (PTs) among most-studied polymers, ordered aggregation solution often induced introduction chiral side chains. This allows using chiroptical spectroscopy, such as circular dichroism, monitor aggregation, but since experimental atomistic demonstrations aggregate arrangements lacking, computational models have been developed identify most likely structure. In this work, we simulate polythiophenes classical molecular dynamics. Standard simulations show formation aggregates with herringbone arrangements, typical polycyclic aromatic hydrocarbon crystals also known for P3HT, polythiophene, rather than H proposed literature. We exploited Hamiltonian Replica Exchange explore a larger portion free energy surface search conformations that would explain experimentally observed response. identified cisoid transoid helical structures intramolecular chirality, without π–stacked commonly suggested, which resulted unstable. Given past studies spectroscopic response these structures, assign genesis chirality polythiophene chains, interactions different chains organized fashion.

Language: Английский

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Multiscale Modeling of Charge Transport in Organic Semiconductors: Assessing the Validity of the Harmonic Approximation for Low-Frequency Vibrations

The Journal of Physical Chemistry C, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 16, 2024

In recent years, the importance of intrinsic disorder in organic semiconductors has gained increasing attention as a factor limiting transport properties these substrates. particular, presence low-frequency phonon modes modulating questions adoption harmonic approximation theoretical descriptions such modes, since large displacements from equilibrium positions are expected. Herein, we have analyzed process several using combination molecular dynamics simulations based on quantum mechanically derived force fields, together with transferable and differentiable deep learning models, trained density functional theory calculations, able to predict transfer integrals their gradients for different substrates, providing ingredients be used within kinetic Monte Carlo prediction charge mobility. obtained fluctuations species crystals approximation, both adopting DFT model, which was also anharmonic strategies exploiting dynamics. Although comparison among approaches evaluate integral difficult interpret, incorporated calculation mobility, compare experiments. Mobilities computed described foundations were consistent agreement experimental literature data, highlighting that, although involved modulation properties, is still appropriate.

Language: Английский

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Computational Design of (B)Chl Models: Structural and Chemical Modifications toward Enriched Properties

The Journal of Physical Chemistry B, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 25, 2024

The functional units of natural photosynthetic systems control the process converting sunlight into chemical energy. In this article, we explore a series chemically and structurally modified bacteriochlorophyll chlorophyll pigments through computational chemistry to evaluate their electronic spectroscopy properties. More specifically, use multiconfigurational time-dependent density theory methods, along with molecular dynamics simulations, compute models' energetics both in an implicit explicit solvent environment. Structural modifications aimed at reducing planarity macrocycle alkyl-bridge anchoring reveal significant role curvature fine-tuning spectral properties, which mimics protein scaffold effects on naturally occurring pigments. Furthermore, substitutions carbonyl group show potential for expanding absorption spectra toward blue region, while incorporating additional double bond decreases efficiency. These insights lay groundwork design novel synthetic pigments, applications artificial light-harvesting more efficient photovoltaic devices.

Language: Английский

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