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The Journal of Chemical Physics

Photon-mediated energy transfer between molecules and atoms in a cavity: A numerical study

Jun Zhang, Shaohong Wang, Mengdi Guo, Xinke Li, Yong‐Chen Xiong, Wang-Huai Zhou

Published Dec 28, 2024• 1 citation
Publisher

Abstract

The molecular energy transfer is crucial for many different physicochemical processes. The efficiency of traditional resonance energy transfer relies on dipole-dipole distance between molecules and becomes negligible when the distance is larger than ∼10 nm, which is difficult to overcome. Cavity polariton, formed when placing molecules inside the cavity, is a promising way to surmount the distance limit. By hybridizing a two-level atom (TLA) and a lithium fluoride (LiF) molecule with a cavity, we numerically simulate the reaction process and the energy transfer between them. Our results show that the TLA can induce a deep potential well, which can be seen as a replica of the potential energy surface of bare LiF, acting as a reservoir to absorb/release the molecular kinetic energy. In addition, the energy transfer shows a molecular nuclear kinetic energy dependent behavior, namely, more nuclear kinetic energy igniting more energy transfer. These findings show us a promising way to manipulate the energy transfer process within the cavity using an intentional TLA, which can also serve as a knob to control the reaction process.

DOI
10.1063/5.0242420

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The molecular energy transfer is crucial for many different physicochemical processes. The efficiency of traditional resonance energy transfer relies on dipole-dipole distance between molecules and becomes negligible when the distance is larger than ∼10 nm, which is difficult to overcome. Cavity polariton, formed when placing molecules inside the cavity, is a promising way to surmount the distance limit. By hybridizing a two-level atom (TLA) and a lithium fluoride (LiF) molecule with a cavity, we numerically simulate the reaction process and the energy transfer between them. Our results show that the TLA can induce a deep potential well, which can be seen as a replica of the potential energy surface of bare LiF, acting as a reservoir to absorb/release the molecular kinetic energy. In addition, the energy transfer shows a molecular nuclear kinetic energy dependent behavior, namely, more nuclear kinetic energy igniting more energy transfer. These findings show us a promising way to manipulate the energy transfer process within the cavity using an intentional TLA, which can also serve as a knob to control the reaction process.
Strong molecule-light interaction enables the control of molecular structures and dynamical processes. A model with a strong laser drive is proposed to greatly enhance the intermolecular distance of resonant energy transfer, where the molecules are strongly driven by an optical cavity. The optimal Rabi frequency and quantum yield of energy transfer are observed, resulting from the trade-off between dipole-dipole interaction and molecule-cavity coupling. When the strong drive at a certain Rabi frequency is applied, a larger spatial range of effective energy transfer and a slower decay rate with the distance compared to the F\"orster mechanism of resonant energy transfer are observed in our model. Our work sheds light on the spectroscopic study of cooperative energy transfer in molecular polaritons.
The field of Polaritonic Chemistry studies molecules strongly coupled to the light field of optical cavities. The resulting modification of the potential energy landscape has been demonstrated to enable control over the chemical and physical properties of materials and molecular ensembles. This thesis extends the Tavis–Cummings model to describe molecules under strong light–matter coupling, incorporating static dipole moments and dipole self-energy contributions derived from the Pauli–Fierz Hamiltonian. These additional terms are shown to be essential for reproducing cavity-modified molecular dynamics and spectra. Simulations on the nuclear wavefunction propagation of MgH+ molecules demonstrate the impact of these terms, while an effective two-level system model accurately captures the behavior of large ensembles. Beyond single excitations, the thesis also explores the higher excitation manifolds of the Tavis-Cummings model, which reveals that allowing for more than a single excitation makes the reaction of the involved polaritons entropically more favorable. Open-system simulations highlight how the coherence of the system's initial state governs decay pathways and enables long-lived energy storage. Finally, a multilevel vibrational model coupled to a two-mode cavity is introduced, where a Raman scheme enables selective mixing of vibrational states. The simulation results show that continuous pumping can drive molecules into specific vibrational states while suppressing electronic excitation, both for single molecules and small ensembles. Together, these results provide new theoretical insights into the mechanisms by which optical cavities reshape molecular energy landscapes. The results suggest approaches for controlling photonic, electronic, and vibrational dynamics in strongly coupled systems, contributing to the theoretical foundation of polariton chemistry.
The rate of energy transfer in donor-acceptor systems can be manipulated via the common interaction with the confined electromagnetic modes of a micro-cavity. We analyze the competition between the near-field short range dipole-dipole energy exchange processes and the cavity mediated long-range interactions in a simplified model consisting of effective two-level quantum emitters that could be relevant for molecules in experiments under cryogenic conditions. We find that free-space collective incoherent interactions, typically associated with sub- and superradiance, can modify the traditional resonant energy transfer scaling with distance. The same holds true for cavity-mediated collective incoherent interactions in a weak-coupling but strong-cooperativity regime. In the strong coupling regime, we elucidate the effect of pumping into cavity polaritons and analytically identify an optimal energy flow regime characterized by equal donor/acceptor Hopfield coefficients in the middle polariton. Finally we quantify the build-up of quantum correlations in the donor-acceptor system via the two-qubit concurrence as a measure of entanglement.
Strong coupling between molecular excitations and quantized electromagnetic fields in optical cavities provides a powerful means to control the physical and chemical properties of molecular systems. Here, we study electron transfer (ET) dynamics in cavity-coupled molecules using the numerically exact hierarchical equations of motion (HEOM) method, which captures nonperturbative and non-Markovian effects beyond standard perturbative theories. We identify distinct resonance and collective effects associated with polariton formation and show that the ET rate saturates in the strong-coupling regime, a feature not captured by perturbative approaches. We further extend the cavity-modified ET model by incorporating the nuclear-coordinate dependence of molecular electric dipole moments, which gives rise to a three-body interaction involving molecular electronic and vibrational degrees of freedom and cavity photons. This vibronic polariton formation leads to non-monotonic, oscillatory dependencies of the ET rate on the light-matter coupling strength and cavity frequency, which we attribute to quantum interference among multiple transfer pathways. These findings establish cavity-modified electron transfer as a multichannel quantum process governed by the interplay of electronic, vibrational, and photonic degrees of freedom.
The rate of energy transfer in donor-acceptor systems can be manipulated via the common interaction with the confined electromagnetic modes of a micro-cavity. We analyze the competition between the near-field short range dipole-dipole energy exchange processes and the cavity mediated long-range interactions in a simplified model consisting of effective two-level quantum emitters that could be relevant for molecules in experiments under cryogenic conditions. We find that free-space collective incoherent interactions, typically associated with sub-and superradiance, can modify the traditional resonant energy transfer scaling with distance. The same holds true for cavity-mediated collective incoherent interactions in a weak-coupling but strong-cooperativity regime. In the strong coupling regime, we elucidate the effect of pumping into cavity polaritons and analytically identify an optimal energy flow regime characterized by equal donor/acceptor Hopfield coefficients in the middle polariton. Finally we quantify the build-up of quantum correlations in the donor-acceptor system via the two-qubit concurrence as a measure of entanglement.
In a molecular system of energy donors and acceptors, resonance energy transfer is the primary mechanism by means of which electronic energy is redistributed between molecules, following the excitation of a donor. Given a suitable geometric configuration it is possible to completely inhibit this energy transfer in such a way that it can only be activated by application of an off-resonant laser beam: this is the principle of optically controlled resonance energy transfer, the basis for an all-optical switch. This paper begins with an investigation of optically controlled energy transfer between a single donor and acceptor molecule, identifying the symmetry and structural constraints and analyzing in detail the dependence on molecular energy level positioning. Spatially correlated donor and acceptor arrays with linear, square, and hexagonally structured arrangements are then assessed as potential configurations for all-optical switching. Built on quantum electrodynamical principles the concept of transfer fidelity, a parameter quantifying the efficiency of energy transportation, is introduced and defined. Results are explored by employing numerical simulations and graphical analysis. Finally, a discussion focuses on the advantages of such energy transfer based processes over all-optical switching of other proposed forms.