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

Physical Chemistry Chemical Physics, Год журнала: 2023, Номер 25(46), С. 31554 - 31577

Опубликована: Янв. 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.

Язык: Английский

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

Journal of Chemical Theory and Computation, Год журнала: 2023, Номер 19(16), С. 5356 - 5368

Опубликована: Июль 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.

Язык: Английский

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Nonadiabatic Derivative Couplings through Multiple Franck–Condon Modes Dictate the Energy Gap Law for Near and Short-Wave Infrared Dye Molecules

The Journal of Physical Chemistry Letters, Год журнала: 2024, Номер 15(7), С. 1802 - 1810

Опубликована: Фев. 8, 2024

Near infrared (NIR, 700–1000 nm) and short-wave (SWIR, 1000–2000 dye molecules exhibit significant nonradiative decay rates from the first singlet excited state to ground state. While these trends can be empirically explained by a simple energy gap law, detailed mechanisms of nearly universal behavior have remained unsettled for many cases. Theoretical experimental results two representative NIR/SWIR reported here clarify key mechanism observed law behavior. It is shown that derivative nonadiabatic coupling terms serve as major pathways processes NIR SWIR vibrational modes other than highest frequency also make contributions rate. This assessment corroborated further theoretical comparison with possible alternative intersystem crossing triplet states data deuterated molecules.

Язык: Английский

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

Journal of Chemical Theory and Computation, Год журнала: 2025, Номер unknown

Опубликована: Март 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.

Язык: Английский

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Nonadiabatic Excited-State Molecular Dynamics Methodologies: Comparison and Convergence

The Journal of Physical Chemistry Letters, Год журнала: 2021, Номер 12(11), С. 2970 - 2982

Опубликована: Март 17, 2021

Direct atomistic simulation of nonadiabatic molecular dynamics is a challenging goal that allows important insights into fundamental physical phenomena. A variety frameworks, ranging from fully quantum treatment nuclei to semiclassical and mixed quantum–classical approaches, were developed. These algorithms are then coupled specific electronic structure techniques. Such diversity lack standardized implementation make it difficult compare the performance different methodologies when treating realistic systems. Here, we three popular methods for large chromophores: Ehrenfest, surface hopping, multiconfigurational Ehrenfest with ab initio multiple cloning (MCE-AIMC). approaches implemented in NEXMD software, which features common computational chemistry model. The resulting comparisons reveal method population relaxation coherent vibronic dynamics. Finally, study numerical convergence MCE-AIMC by considering number trajectories, thresholds, Gaussian wavepacket width. Our results provide helpful reference data selecting an optimal methodology simulating excited-state

Язык: Английский

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NWChem: Recent and Ongoing Developments

Journal of Chemical Theory and Computation, Год журнала: 2023, Номер 19(20), С. 7077 - 7096

Опубликована: Июль 17, 2023

This paper summarizes developments in the NWChem computational chemistry suite since last major release (NWChem 7.0.0). Specifically, we focus on functionality, along with input blocks, that is accessible current stable 7.2.0) and "master" development branch, interfaces to quantum computing simulators, external libraries, github repository, containerization of executable images. Some ongoing will be available near future are also discussed.

Язык: Английский

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An Ab Initio Multiple Cloning Method for Non-Adiabatic Excited-State Molecular Dynamics in NWChem

Journal of Chemical Theory and Computation, Год журнала: 2021, Номер 17(6), С. 3629 - 3643

Опубликована: Май 20, 2021

The recently developed ab initio multiple cloning (AIMC) approach based on the multiconfigurational Ehrenfest (MCE) method provides a powerful and accurate way of describing excited-state dynamics molecular systems. AIMC is controlled approximation to nonadiabatic with particular strength in proper description decoherence effects because branching vibrational wavepackets at level crossing. Here, we report new implementation algorithm open source NWChem computational chemistry program. framework combines linear-response time-dependent density functional theory mean-field determine equations motion for classical trajectories. multidimensional wave function decomposed into superposition Gaussian coherent states guided by trajectories (i.e., MCE approach), which can clone fully quantum mechanical amplitudes phases. By using an efficient time-derivative coupling within method, all observables are calculated on-the-fly process. As representative example, apply our study ultrafast photoinduced electronic energy transfer pyridine molecule. procedure coherence, relaxation unidirectional discussed. This high-level simulating photoexcited complex systems experimentally relevant spectroscopic probes, such as nonlinear optical X-ray signals.

Язык: Английский

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Transient-Absorption Spectroscopy of Dendrimers via Nonadiabatic Excited-State Dynamics Simulations

Chemical Science, Год журнала: 2024, Номер 15(33), С. 13250 - 13261

Опубликована: Янв. 1, 2024

The efficiency of light-harvesting and energy transfer in multi-chromophore ensembles underpins natural photosynthesis.

Язык: Английский

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Fermi’s Golden Rule Rate Expression for Transitions Due to Nonadiabatic Derivative Couplings in the Adiabatic Basis

Journal of Chemical Theory and Computation, Год журнала: 2025, Номер 21(4), С. 1850 - 1864

Опубликована: Фев. 13, 2025

Starting from a general molecular Hamiltonian expressed in the basis of adiabatic electronic and nuclear position states, where compact complete expression for nonadiabatic derivative coupling (NDC) term is obtained, we provide analysis Fermi's golden rule (FGR) rate transitions between states. We then consider quasi-adiabatic approximation that uses crude states NDC couplings, both evaluated at minimum potential energy configuration initial state, definition zeroth first-order terms Hamiltonian. Although application this rather limited, it allows deriving FGR without further while accounting non-Condon contribution to arising momentum operators its with vibronic displacements. For generic widely used model all degrees freedom environmental effects are represented as linearly coupled harmonic oscillators, derive closed-form requires only Fourier transform. The resulting includes quadratic contributions their couplings Franck–Condon modes, which require evaluation two additional bath spectral densities addition conventional one appears typical theory based on Condon approximation. Model calculations case vibrations consist sharp high-frequency mode an Ohmic density illustrate new features implications expression. apply our theoretical nonradiative decay first excited singlet state azulene, illustrates utility results.

Язык: Английский

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Pinning Excited State Self-Trapping with All-Benzene Trefoil Knot

The Journal of Physical Chemistry Letters, Год журнала: 2025, Номер unknown, С. 4228 - 4235

Опубликована: Апрель 21, 2025

The synthesis of novel carbon nanostructures with unique topologies expands the landscape organic molecules, introducing new chemical properties and potential applications. Carbon nanorings, composed cyclic paraphenylene (CPP) chains, serve as a versatile scaffold for designing materials molecular architectures that impact their optical photoinduced dynamics. These alter balance between competing π-conjugation effects, high bending strain energies, steric hindrances imposed by rearrangement structures. Here, we explore dynamics all-benzene trefoil knot using nonadiabatic excited-state We show how its absorption spectra can be modeled particle in box constrained to geometry, analyze internal conversion process following photoexcitation. Our findings reveal an exciton intraring migration governed winding chain, ultimately leading self-trapping at specific curvature regions knot. This behavior contrasts nondeterministic corresponding CPP, where localization occurs randomly across different phenylene units. results highlight ability knots control through curvature, tension, planarization positioning these promising candidates future technological precisely manipulate electronic characteristics is essential developing more efficient devices.

Язык: Английский

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