Analysis of the classical trajectory treatment of photon dynamics for polaritonic phenomena

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

doi:10.1063/5.0079379

Cited by 12 publications

(11 citation statements)

References 50 publications

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“…Under VSC, the recently developed classical cavity molecular dynamics (CavMD) , approach treats the infrared cavity mode as an additional “nuclear” coordinate, and a fully classical simulation of the coupled cavity-nuclear system has been shown to qualitatively capture nonequilibrium dynamics under collective VSC arising from an ensemble of molecules coupled to the infrared cavity. Other methods such as the exact factorization and multiconfigurational time-dependent Hartree method (MCTDH) also provide an accurate description of quantum effects under ESC or VSC. In addition to a fully quantum or classical treatment of the coupled cavity-molecular system, a variety of semiclassical treatments of the light–matter system − have also been shown to have the potential to accurately predict many light-involved processes from weak coupling to ESC.…”

Section: Introductionmentioning

confidence: 99%

Semiclassical Real-Time Nuclear-Electronic Orbital Dynamics for Molecular Polaritons: Unified Theory of Electronic and Vibrational Strong Couplings

Tao

Hammes‐Schiffer

2022

J. Chem. Theory Comput.

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Molecular polaritons have become an emerging platform for remotely controlling molecular properties through strong light–matter interactions. Herein, a semiclassical approach is developed for describing molecular polaritons by self-consistently propagating the real-time dynamics of classical cavity modes and a quantum molecular subsystem described by the nuclear-electronic orbital (NEO) method, where electrons and specified nuclei are treated quantum mechanically on the same level. This semiclassical real-time NEO approach provides a unified description of electronic and vibrational strong couplings and describes the impact of the cavity on coupled nuclear-electronic dynamics while including nuclear quantum effects. For a single o-hydroxybenzaldehyde molecule under electronic strong coupling, this approach shows that the cavity suppression of excited state intramolecular proton transfer is influenced not only by the polaritonic potential energy surface but also by the time scale of the chemical reaction. This work provides the foundation for exploring collective strong coupling in nuclear-electronic quantum dynamical systems within optical cavities.

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Section: Introductionmentioning

confidence: 99%

Semiclassical Real-Time Nuclear-Electronic Orbital Dynamics for Molecular Polaritons: Unified Theory of Electronic and Vibrational Strong Couplings

Tao

Hammes‐Schiffer

2022

J. Chem. Theory Comput.

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“…Understanding how the collective polaritonic state can induce a significant modification of local molecular properties, especially the chemical reaction rates, requires methods beyond conventional chemical modeling of molecules. Many different theoretical efforts, including the study of classical or quantum mechanical model systems, − quantum-electrodynamical electronic structure theory, − exaction factorization, and the multiconfigurational time-dependent Hartree method (MCTDH), have been directed toward modeling vibrational polaritons and their chemical effects.…”

Section: Introductionmentioning

confidence: 99%

QM/MM Modeling of Vibrational Polariton Induced Energy Transfer and Chemical Dynamics

Hammes‐Schiffer

2022

J. Am. Chem. Soc.

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Vibrational strong coupling (VSC) provides a novel means to modify chemical reactions and energy transfer pathways. To efficiently model chemical dynamics under VSC in the collective regime, herein a hybrid quantum mechanical/ molecular mechanical (QM/MM) cavity molecular dynamics (CavMD) scheme is developed and applied to an experimentally studied chemical system. This approach can achieve linear scaling with respect to the number of molecules for a dilute solution under VSC by assuming that each QM solute molecule is surrounded by an independent MM solvent bath. Application of this approach to a dilute solution of Fe(CO) 5 in n-dodecane under VSC demonstrates polariton dephasing to the dark modes and polariton-enhanced molecular nonlinear absorption. These simulations predict that strongly exciting the lower polariton may provide an energy transfer pathway that selectively excites the equatorial CO vibrations rather than the axial CO vibrations. Moreover, these simulations also directly probe the cavity effect on the dynamics of the Fe(CO) 5 Berry pseudorotation reaction for comparison to recent two-dimensional infrared spectroscopy experiments. This theoretical approach is applicable to a wide range of other polaritonic systems and provides a tool for exploring the use of VSC for selective infrared photochemistry.

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“…Work is in progress to extend the self-consistent XF-based MQC methods to the polaritonic case for practical applications. To account for many cavity modes, a classical Ehrenfest treatment for the dynamics of the photonic system has been explored [99], and using the XF with the marginal as the photonic displacement coordinate could explain the general underestimation of photon numbers in this approach [100] through comparing the exact potential driving the photons with that underlying the Ehrenfest approach. A further useful factorization could be Ψ(r, R, q, t) = χ(R, q, t)Φ R,q (r, t) since this would yield a TDSE for both the nuclear and photonic systems in which the potential "exactifies" the concept of cavity-BO surfaces introduced in ref.…”

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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Analysis of the classical trajectory treatment of photon dynamics for polaritonic phenomena

Cited by 12 publications

References 50 publications

Semiclassical Real-Time Nuclear-Electronic Orbital Dynamics for Molecular Polaritons: Unified Theory of Electronic and Vibrational Strong Couplings

Semiclassical Real-Time Nuclear-Electronic Orbital Dynamics for Molecular Polaritons: Unified Theory of Electronic and Vibrational Strong Couplings

QM/MM Modeling of Vibrational Polariton Induced Energy Transfer and Chemical Dynamics

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

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