Tensorial properties via the neuroevolution potential framework: Fast simulation of infrared and Raman spectra DOI Creative Commons
Nan Xu,

Petter Rosander,

C. Schäfer

и другие.

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

Опубликована: Янв. 1, 2023

Infrared and Raman spectroscopy are widely used for the characterization of gases, liquids, solids, as spectra contain a wealth information concerning in particular dynamics these systems. Atomic scale simulations can be to predict such but often severely limited due high computational cost or need strong approximations that limit application range reliability. Here, we introduce machine learning (ML) accelerated approach addresses shortcomings provides significant performance boost terms data efficiency compared earlier ML schemes. To this end, generalize neuroevolution potential enable prediction rank one two tensors obtain tensorial (TNEP) scheme. We apply resulting framework construct models dipole moment, polarizability, susceptibility molecules, show our compares favorably with several from literature respect accuracy efficiency. Finally, demonstrate TNEP infrared liquid water, molecule (PTAF-), prototypical perovskite anharmonicity (BaZrO3). The is implemented free open source software package GPUMD, which makes methodology readily available scientific community.

Язык: Английский

Analytic model reveals local molecular polarizability changes induced by collective strong coupling in optical cavities DOI

Jacob Horak,

Dominik Sidler, Thomas Schnappinger

и другие.

Physical Review Research, Год журнала: 2025, Номер 7(1)

Опубликована: Март 5, 2025

Despite recent numerical evidence, one of the fundamental theoretical mysteries polaritonic chemistry is how and if collective strong coupling can induce local changes electronic structure to modify chemical properties. Here we present nonperturbative analytic results for a model system consisting an ensemble N harmonic molecules under vibrational (VSC) that alters our understanding this question. By applying cavity Born-Oppenheimer partitioning on Pauli-Fierz Hamiltonian in dipole approximation, dressed many-molecule problem be solved nonperturbatively analytically dilute limit, i.e., self-consistent solution with mean-field Hartree-product wave function becomes exact. We discover molecular polarizabilities are modified even case vanishingly small single-molecule couplings. Consequently, polarization mechanism persists large-N limit. In contrast, perturbative calculation based uncoupled leads qualitatively erroneous scaling behavior vanishing effects large-N Nevertheless, exact (self-consistent) determined from simulations instead. Our observations demonstrate hitherto existing collective-scaling arguments insufficient they pave way refined single- (or few-)molecule strong-coupling systems coupling. Published by American Physical Society 2025

Язык: Английский

Процитировано

3
Collective Strong Coupling Modifies Aggregation and Solvation DOI Creative Commons
Matteo Castagnola, Tor S. Haugland, Enrico Ronca

и другие.

The Journal of Physical Chemistry Letters, Год журнала: 2024, Номер 15(5), С. 1428 - 1434

Опубликована: Янв. 30, 2024

Intermolecular (Coulombic) interactions are pivotal for aggregation, solvation, and crystallization. We demonstrate that the collective strong coupling of several molecules to a single optical mode results in notable changes molecular excitations around perturbed molecule, thus representing an impurity otherwise ordered system. A competition between short-range coulombic long-range photonic correlations inverts local transition density polaritonic state, suggesting polarizability solvation shell. Our provide alternative perspective on recent work chemistry pave way rigorous treatment cooperative effects

Язык: Английский

Процитировано

14
Tensorial Properties via the Neuroevolution Potential Framework: Fast Simulation of Infrared and Raman Spectra DOI Creative Commons
Nan Xu,

Petter Rosander,

C. Schäfer

и другие.

Journal of Chemical Theory and Computation, Год журнала: 2024, Номер 20(8), С. 3273 - 3284

Опубликована: Апрель 4, 2024

Infrared and Raman spectroscopy are widely used for the characterization of gases, liquids, solids, as spectra contain a wealth information concerning, in particular, dynamics these systems. Atomic scale simulations can be to predict such but often severely limited due high computational cost or need strong approximations that limit application range reliability. Here, we introduce machine learning (ML) accelerated approach addresses shortcomings provides significant performance boost terms data efficiency compared with earlier ML schemes. To this end, generalize neuroevolution potential enable prediction rank one two tensors obtain tensorial (TNEP) scheme. We apply resulting framework construct models dipole moment, polarizability, susceptibility molecules, solids show our compares favorably several from literature respect accuracy efficiency. Finally, demonstrate TNEP infrared liquid water, molecule (PTAF

Язык: Английский

Процитировано

13
A Quantum Chemistry Approach to Linear Vibro-Polaritonic Infrared Spectra with Perturbative Electron–Photon Correlation DOI Creative Commons
Eric W. Fischer,

Jan A. Syska,

Peter Saalfrank

и другие.

The Journal of Physical Chemistry Letters, Год журнала: 2024, Номер 15(8), С. 2262 - 2269

Опубликована: Фев. 21, 2024

In the vibrational strong coupling (VSC) regime, molecular vibrations and resonant low-frequency cavity modes form light-matter hybrid states, polaritons, with characteristic infrared (IR) spectroscopic signatures. Here, we introduce a quantum chemistry-based computational scheme for linear IR spectra of polaritons in polyatomic molecules, which perturbatively accounts nonresonant electron-photon interactions under VSC. Specifically, formulate Born-Oppenheimer perturbation theory (CBO-PT) response approach, provides an approximate but systematic description such correlation effects VSC scenarios while relying on ab initio chemistry methods. We identify relevant at second order CBO-PT, manifest as static polarizability-dependent Hessian corrections emerging intensity component providing access to transmission commonly measured vibro-polaritonic chemistry. Illustratively, address CO2 Fe(CO)5 models sound agreement nonperturbative CBO theory.

Язык: Английский

Процитировано

8
Resonance theory of vibrational strong coupling enhanced polariton chemistry and the role of photonic mode lifetime DOI Creative Commons
Wenxiang Ying, Pengfei Huo

Communications Materials, Год журнала: 2024, Номер 5(1)

Опубликована: Июнь 28, 2024

Abstract Recent experiments demonstrate polaritons under the vibrational strong coupling (VSC) regime can modify chemical reactivity. Here, we present a complete theory of VSC-modified rate constants when single molecule to an optical cavity, where role photonic mode lifetime is understood. The analytic expression exhibits sharp resonance behavior, maximum constant reached cavity frequency matches vibration frequency. explains why VSC modification closely resembles spectra outside cavity. Further, discussed temperature dependence constants. agrees well with numerically exact hierarchical equations motion (HEOM) simulations for all explored regimes. Finally, condition at normal incidence considering in-plane momentum inside Fabry-Pérot

Язык: Английский

Процитировано

8
Controlling Plasmonic Catalysis via Strong Coupling with Electromagnetic Resonators DOI Creative Commons
Jakub Fojt, Paul Erhart, C. Schäfer

и другие.

Nano Letters, Год журнала: 2024, Номер unknown

Опубликована: Сен. 12, 2024

Plasmonic excitations decay within femtoseconds, leaving nonthermal (often referred to as "hot") charge carriers behind that can be injected into molecular structures trigger chemical reactions are otherwise out of reach─a process known plasmonic catalysis. In this Letter, we demonstrate strong coupling between resonator and nanoparticles used control the spectral overlap excitation energy injection nearby molecules. Our atomistic description couples real-time density-functional theory self-consistently an electromagnetic structure via radiation-reaction potential. Control over provides then additional knob for nonintrusively enhancing catalysis, here more than 6-fold, dynamically reacting deterioration catalyst─a new facet modern

Язык: Английский

Процитировано

4
Microfluidics and Nanofluidics in Strong Light–Matter Coupling Systems DOI Creative Commons
Evelyn Granizo, Irina Kriukova, Pedro Escudero‐Villa

и другие.

Nanomaterials, Год журнала: 2024, Номер 14(18), С. 1520 - 1520

Опубликована: Сен. 19, 2024

The combination of micro- or nanofluidics and strong light-matter coupling has gained much interest in the past decade, which led to development advanced systems devices with numerous potential applications different fields, such as chemistry, biosensing, material science. Strong is achieved by placing a dipole (e.g., an atom molecule) into confined electromagnetic field, molecular transitions being resonance field strength exceeding average dissipation rate. Despite intense research encouraging results this some challenges still need be overcome, related fabrication nano- microscale optical cavities, stability, scaling up production, sensitivity, signal-to-noise ratio, real-time control monitoring. goal paper summarize recent developments nanofluidic employing coupling. An overview various methods techniques used achieve presented, preceded brief outline fundamentals optofluidics operating regime. these integrated sensing, optofluidics, quantum technologies are explored. prospects rapidly developing discussed.

Язык: Английский

Процитировано

3
Advances in modeling complex materials: The rise of neuroevolution potentials DOI Open Access
Penghua Ying, Cheng Qian, Rui Zhao

и другие.

Chemical Physics Reviews, Год журнала: 2025, Номер 6(1)

Опубликована: Март 1, 2025

Interatomic potentials are essential for driving molecular dynamics (MD) simulations, directly impacting the reliability of predictions regarding physical and chemical properties materials. In recent years, machine-learned (MLPs), trained against first-principles calculations, have become a new paradigm in materials modeling as they provide desirable balance between accuracy computational cost. The neuroevolution potential (NEP) approach, implemented open-source GPUMD software, has emerged promising potential, exhibiting impressive exceptional efficiency. This review provides comprehensive discussion on methodological practical aspects NEP along with detailed comparison other representative state-of-the-art MLP approaches terms training accuracy, property prediction, We also demonstrate application approach to perform accurate efficient MD addressing complex challenges that traditional force fields typically cannot tackle. Key examples include structural liquid amorphous materials, order alloy systems, phase transitions, surface reconstruction, material growth, primary radiation damage, fracture two-dimensional nanoscale tribology, mechanical behavior compositionally alloys under various loadings. concludes summary perspectives future extensions further advance this rapidly evolving field.

Язык: Английский

Процитировано

0
The influence of core-shell chemical ordering on the generation and transfer of hot carriers DOI
Junais Habeeb Mokkath

Materials Today Chemistry, Год журнала: 2025, Номер 45, С. 102693 - 102693

Опубликована: Апрель 1, 2025

Язык: Английский

Процитировано

0
Direct Observation of Polaritonic Chemistry by Nuclear Magnetic Resonance Spectroscopy DOI Creative Commons

Thomas W. Ebbesen,

Bianca Patrahau,

Maciej Piejko

и другие.

Опубликована: Дек. 8, 2023

Polaritonic chemistry is emerging as a powerful approach to modifying the properties and reactivity of molecules materials. However, probing how electronics dynamics molecular systems change under strong coupling has been challenging due narrow range spectroscopic techniques that can be applied in situ. Here we develop microfluidic optical cavities for vibrational (VSC) are compatible with nuclear magnetic resonance (NMR) spectroscopy using standard liquid NMR tubes. VSC shown influence equilibrium between two conformations balance sensitive dispersion forces, revealing clear constant VSC. In all compounds studied, does not induce detectable changes chemical shifts, J-couplings, or spin-lattice relaxation times. This unexpected finding indicates substantially affect electron density distributions, turn profound implications possible mechanisms at play polaritonic suggests emergence collective behavior critical.

Язык: Английский

Процитировано

7