Theoretical Advances in Polariton Chemistry and Molecular Cavity Quantum Electrodynamics

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(16), P. 9786 - 9879

Published: Aug. 8, 2023

When molecules are coupled to an optical cavity, new light-matter hybrid states, so-called polaritons, formed due quantum interactions. With the experimental demonstrations of modifying chemical reactivities by forming polaritons under strong interactions, theorists have been encouraged develop methods simulate these systems and discover strategies tune control reactions. This review summarizes some exciting theoretical advances in polariton chemistry, ranging from fundamental framework computational techniques applications spanning photochemistry vibrational coupling. Even though theory interactions goes back midtwentieth century, gaps knowledge molecular electrodynamics (QED) only recently filled. We recent made resolving gauge ambiguities, correct form different QED Hamiltonians gauges, their connections various optics models. Then, we developed ab initio approaches which can accurately describe states a realistic molecule-cavity system. then discuss using method advancements. advancements where cavity is resonant electronic transitions nonadiabatic excited state dynamics enable photochemical reactivities. resonance tuned vibrations instead, ground-state reaction modifications demonstrated experimentally, its mechanistic principle remains unclear. present progress this mystery. Finally, understanding collective coupling regime between light matter, many collectively couple single mode or modes. also lay out current challenges explain observed results. hope that will serve as useful document for anyone who wants become familiar with context chemistry thus significantly benefit entire community.

Language: Английский

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Ab initio nonadiabatic molecular dynamics of charge carriers in metal halide perovskites

Nanoscale, Journal Year: 2021, Volume and Issue: 13(23), P. 10239 - 10265

Published: Jan. 1, 2021

Atomistic details govern quantum dynamics of charge carriers in metal halide perovskites, which exhibit properties solid state and molecular semiconductors, as revealed by time-domain density functional theory nonadiabatic dynamics.

Language: Английский

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Newton-X Platform: New Software Developments for Surface Hopping and Nuclear Ensembles

Journal of Chemical Theory and Computation, Journal Year: 2022, Volume and Issue: 18(11), P. 6851 - 6865

Published: Oct. 4, 2022

Newton-X is an open-source computational platform to perform nonadiabatic molecular dynamics based on surface hopping and spectrum simulations using the nuclear ensemble approach. Both are among most common methodologies in chemistry for photophysical photochemical investigations. This paper describes main features of these methods how they implemented Newton-X. It emphasizes newest developments, including zero-point-energy leakage correction, complex-valued potential energy surfaces, induced by incoherent light, machine-learning potentials, exciton multiple chromophores, supervised unsupervised machine learning techniques. interfaced with several third-party quantum-chemistry programs, spanning a broad electronic structure methods.

Language: Английский

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Theory and modeling of light-matter interactions in chemistry: current and future

Physical Chemistry Chemical Physics, Journal Year: 2023, Volume and Issue: 25(46), P. 31554 - 31577

Published: Jan. 1, 2023

Light-matter interaction not only plays an instrumental role in characterizing materials' properties via various spectroscopic techniques but also provides a general strategy to manipulate material the design of novel nanostructures. This perspective summarizes recent theoretical advances modeling light-matter interactions chemistry, mainly focusing on plasmon and polariton chemistry. The former utilizes highly localized photon, plasmonic hot electrons, local heat drive chemical reactions. In contrast, chemistry modifies potential energy curvatures bare electronic systems, hence their forming hybrid states, so-called polaritons. starts with basic background interactions, molecular quantum electrodynamics theory, challenges Then, are described, future directions toward multiscale simulations interaction-mediated discussed.

Language: Английский

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SPADE 1.0: A Simulation Package for Non-Adiabatic Dynamics in Extended Systems

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

Published: March 24, 2025

Nonadiabatic molecular dynamics (NAMD) simulations are crucial for revealing the underlying mechanisms of photochemical and photophysical processes. Typical NAMD simulation software packages rely on on-the-fly ab initio electronic structure nonadiabatic coupling calculations, thus become challenging when dealing with large complex systems. We here introduce a new Simulation Package non-Adiabatic Dynamics in Extended systems (SPADE), which is designed to address limitations traditional surface hopping methods these problems. By design, SPADE enables users define arbitrary quasi-diabatic Hamiltonians through parametrized functions incorporates variety algorithms (e.g., global flux probabilities, crossing decoherence corrections), can realize efficient reliable without using couplings at all. All employed expressions diabatic Hamiltonian matrix elements be flexibly set input files. mainly written Fortran based modular design has great capacity further implementation methods. used simulate both model atomistic as long proper provided. As demonstrations, series representative models studied show main features capabilities.

Language: Английский

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Quantum and semiclassical dynamical studies of nonadiabatic processes in solution: achievements and perspectives

Physical Chemistry Chemical Physics, Journal Year: 2021, Volume and Issue: 23(14), P. 8181 - 8199

Published: Jan. 1, 2021

We concisely review the most used methodological approaches to model nonadiabatic dynamics in isotropic solutions and their applications.

Language: Английский

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Deep learning of dynamically responsive chemical Hamiltonians with semiempirical quantum mechanics

Proceedings of the National Academy of Sciences, Journal Year: 2022, Volume and Issue: 119(27)

Published: July 1, 2022

Conventional machine-learning (ML) models in computational chemistry learn to directly predict molecular properties using quantum only for reference data. While these heuristic ML methods show quantum-level accuracy with speeds several orders of magnitude faster than traditional methods, they suffer from poor extensibility and transferability; i.e., their degrades on large or new chemical systems. Incorporating frameworks into the solves this problem. Here we take structure semiempirical mechanics (SEQM) construct dynamically responsive Hamiltonians. SEQM use empirical parameters fitted experimental reduced-order Hamiltonians, facilitating much calculations ab initio but compromised accuracy. By replacing static machine-learned dynamic values inferred local environment, greatly improve methods. Trained energies atomic forces, generated Hamiltonian a strong correlation hybridization bonding. about 60,000 small organic conformers, resulting model retains interpretability, extensibility, transferability when testing larger systems predicting various properties. Overall, work demonstrates virtues incorporating physics-based descriptions develop that are simultaneously accurate, transferable, interpretable.

Language: Английский

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Fewest switches surface hopping with Baeck-An couplings

Open Research Europe, Journal Year: 2022, Volume and Issue: 1, P. 49 - 49

Published: March 9, 2022

In the Baeck-An (BA) approximation, first-order nonadiabatic coupling vectors are given in terms of adiabatic energy gaps and second derivative with respect to coordinate. this paper, a time-dependent (TD) BA approximation is derived, where couplings computed from their time-derivatives. TD-BA can be directly used fewest switches surface hopping, enabling dynamics any electronic structure methods able provide excitation energies gradients. Test results hopping for ethylene fulvene show that delivers qualitatively correct picture semiquantitative agreement reference data exact couplings. Nevertheless, does not perform well situations conjugating strong small velocities. Considered uncertainties method, could competitive approach inexpensive, exploratory trajectories ensemble. We also assessed potential use density functional theory (TDDFT), but encouraging due singlet instabilities near crossing seam ground state.

Language: Английский

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NEXMD v2.0 Software Package for Nonadiabatic Excited State Molecular Dynamics Simulations

Journal of Chemical Theory and Computation, Journal Year: 2023, Volume and Issue: 19(16), P. 5356 - 5368

Published: July 28, 2023

We present NEXMD version 2.0, the second release of (Nonadiabatic EXcited-state Molecular Dynamics) software package. Across a variety new features, v2.0 incorporates implementations two hybrid quantum-classical dynamics methods, namely, Ehrenfest (EHR) and Ab-Initio Multiple Cloning sampling technique for Multiconfigurational quantum (MCE-AIMC or simply AIMC), which are alternative options to previously implemented trajectory surface hopping (TSH) method. To illustrate these methodologies, we outline direct comparison three methods as in same framework, discussing their weaknesses strengths, using modeled photodynamics polyphenylene ethylene dendrimer building block representative example. also describe expanded normal-mode analysis constraints both ground excited states, newly allow deeper main vibrational motions involved vibronic dynamics. Overall, expands range applications larger multichromophore organic molecules photophysical processes involving coherences persistent couplings between electronic states nuclear velocity.

Language: Английский

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Prediction challenge: First principles simulation of the ultrafast electron diffraction spectrum of cyclobutanone

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 160(13)

Published: April 4, 2024

Computer simulation has long been an essential partner of ultrafast experiments, allowing the assignment microscopic mechanistic detail to low-dimensional spectroscopic data. However, ability theory make a priori predictions experimental results is relatively untested. Herein, as part community challenge, we attempt predict signal upcoming photochemical experiment using state-of-the-art in context preexisting Specifically, employ ab initio Ehrenfest with collapse block mixed quantum-classical simulations describe real-time evolution electrons and nuclei cyclobutanone following excitation 3s Rydberg state. The gas-phase electron diffraction (GUED) simulated for direct comparison at Stanford Linear Accelerator Laboratory. Following initial ring-opening, dissociation via two distinct channels observed: C3 channel, producing cyclopropane CO, C2 CH2CO C2H4. Direct calculations GUED indicate how ring-opened intermediate, products, products can be discriminated signal. We also report analysis anticipated errors our predictions: without knowledge result, which features spectrum do feel confident have predicted correctly, might wrong?

Language: Английский

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