Case studies of the time-dependent potential energy surface for dynamics in cavities

Martinez, Phillip; Rosenzweig, Bart; Hoffmann, Norah M.; Lacombe, Lionel; Maitra, Neepa T.

doi:10.1063/5.0033386

Cited by 19 publications

(12 citation statements)

References 56 publications

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“…48 This model has been used to investigate how cavity can influence proton-coupled electron transfer reaction with the exact factorization approach. 48,60,61 The PES of SM2 is asymmetric and there is an avoid crossing near R = 2.0 a.u.. The photon energy we use is 0.1 a.u., which causes a light- When the coupling is weak (g c = 0.001), the polaritonic PESs (Fig.…”

Section: Resultsmentioning

confidence: 99%

Nuclear Gradient Expressions for Molecular Cavity Quantum Electrodynamics Simulations using Mixed Quantum-Classical Methods

Zhou

Mandal

et al. 2022

Preprint

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We derive a rigorous nuclear gradient for a molecule-cavity hybrid system using the Quantum Electrodynamics Hamiltonian. We treat the electronic-photonic DOFs as the quantum subsystem, and the nuclei as the classical subsystem. Using the adiabatic basis for the electronic DOF and the Fock basis for the photonic DOF, and requiring the total energy conservation of this mixed quantum-classical system, we derived the rigorous nuclear gradient for the molecule-cavity hybrid system, which is naturally connected to the approximate gradient under the Jaynes-Cummings approximation. The nuclear gradient expression can be readily used in any mixed quantum-classical simulations and will allow one to perform the non-adiabatic on-the-fly simulation of polariton quantum dynamics. The theoretical developments in this work could significantly benefit the polariton quantum dynamics community with a rigorous nuclear gradient of the molecule-cavity hybrid system and have a broad impact on the future non-adiabatic simulations of polariton quantum dynamics.

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Section: Resultsmentioning

confidence: 99%

Nuclear Gradient Expressions for Molecular Cavity Quantum Electrodynamics Simulations using Mixed Quantum-Classical Methods

Zhou

Mandal

et al. 2022

Preprint

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“…We will discuss this in more detail below. We note that there are also alternative schemes, such as exact factorization approaches, ,− that we will not go into further detail here.…”

Section: First-principles Approaches To Nonrelativistic Qedmentioning

confidence: 99%

Understanding Polaritonic Chemistry from Ab Initio Quantum Electrodynamics

Ruggenthaler,

Sidler,

Rubio

2023

Chem. Rev.

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In this review, we present the theoretical foundations and first-principles frameworks to describe quantum matter within quantum electrodynamics (QED) in the low-energy regime, with a focus on polaritonic chemistry. By starting from fundamental physical and mathematical principles, we first review in great detail ab initio nonrelativistic QED. The resulting Pauli-Fierz quantum field theory serves as a cornerstone for the development of (in principle exact but in practice) approximate computational methods such as quantum-electrodynamical density functional theory, QED coupled cluster, or cavity Born−Oppenheimer molecular dynamics. These methods treat light and matter on equal footing and, at the same time, have the same level of accuracy and reliability as established methods of computational chemistry and electronic structure theory. After an overview of the key ideas behind those ab initio QED methods, we highlight their benefits for understanding photon-induced changes of chemical properties and reactions. Based on results obtained by ab initio QED methods, we identify open theoretical questions and how a so far missing detailed understanding of polaritonic chemistry can be established. We finally give an outlook on future directions within polaritonic chemistry and first-principles QED.

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“…[97] showed how its features result in the suppression of proton-coupled electron-transfer in a model system, unlike the polaritonic surfaces. To properly model the complex systems used in the experiments, approximations such as MQC would be required, and running classical dynamics on the exact TDPES [98] gives a big improvement than when using simply the weighted polaritonic surface. Work is in progress to extend the self-consistent XF-based MQC methods to the polaritonic case for practical applications.…”

Section: Xf Adventures In Different Realmsmentioning

confidence: 99%

Exact Factorization Adventures: A Promising Approach for Non-Bound States

2022

Self Cite

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Modeling the dynamics of non-bound states in molecules requires an accurate description of how electronic motion affects nuclear motion and vice-versa. The exact factorization (XF) approach offers a unique perspective, in that it provides potentials that act on the nuclear subsystem or electronic subsystem, which contain the effects of the coupling to the other subsystem in an exact way. We briefly review the various applications of the XF idea in different realms, and how features of these potentials aid in the interpretation of two different laser-driven dissociation mechanisms. We present a detailed study of the different ways the coupling terms in recently-developed XF-based mixed quantum-classical approximations are evaluated, where either truly coupled trajectories, or auxiliary trajectories that mimic the coupling are used, and discuss their effect in both a surface-hopping framework as well as the rigorously-derived coupled-trajectory mixed quantum-classical approach.

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Case studies of the time-dependent potential energy surface for dynamics in cavities

Cited by 19 publications

References 56 publications

Nuclear Gradient Expressions for Molecular Cavity Quantum Electrodynamics Simulations using Mixed Quantum-Classical Methods

Nuclear Gradient Expressions for Molecular Cavity Quantum Electrodynamics Simulations using Mixed Quantum-Classical Methods

Understanding Polaritonic Chemistry from Ab Initio Quantum Electrodynamics

Exact Factorization Adventures: A Promising Approach for Non-Bound States

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