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arXiv:2005.00201

Polarized Fock States for Polariton Photochemistry

Arkajit Mandal, Sebastian Montillo Vega, Pengfei Huo

Published May 1, 2020• 1 citation
arXivHTMLPDF

Abstract

We use the polarized Fock states to describe the coupled molecule-cavity hybrid system in quantum electrodynamics. The molecular permanent dipoles polarize the photon field by displacing its vector potential, leading to non-orthogonality between the Fock states of two different polarized photon fields. These polarized Fock states allow an intuitive understanding of several new phenomena that go beyond the prediction of the quantum Rabi model, and at the same time, offer numerical convenience to converge the results. We further exploit this non-orthogonality to generate multiple photons from a single electronic excitation (downconversion) and control the photochemical reactivity.

DOI
10.48550/arxiv.2005.00201

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We use the polarized Fock states to describe the coupled molecule-cavity hybrid system in quantum electrodynamics. The molecular permanent dipoles polarize the photon field by displacing its vector potential, leading to non-orthogonality between the Fock states of two different polarized photon fields. These polarized Fock states allow an intuitive understanding of several new phenomena that go beyond the prediction of the quantum Rabi model, and at the same time, offer numerical convenience to converge the results. We further exploit this non-orthogonality to generate multiple photons from a single electronic excitation (downconversion) and control the photochemical reactivity.
We present a new theoretical framework, polarized Fock states (PFSs), to describe the coupled molecule-cavity hybrid system in quantum electrodynamics. Through the quantum light-matter interactions under the dipole Gauge, the molecular permanent dipoles polarize the photon field by displacing the photonic coordinate. Hence, it is convenient to use these shifted Fock states (termed the PFSs) to describe light-matter interactions under the strong coupling regimes. These PFSs are nonorthogonal to each other and are light-matter entangled states. They allow an intuitive understanding of several phenomena that go beyond the prediction of the quantum Rabi model, while also offering numerical convenience to converge the results with much fewer states. With this powerful new theoretical framework, we explain how molecular permanent dipoles lead to the generation of multiple photons from a single electronic excitation (down-conversion), effectively achieving the dynamical Casimir effect through the nuclear vibration instead of cavity mirror oscillations.
We address topics related to molecules coupled to quantum radiation. The formalism of light-matter interaction is different for classical and quantum fields, but some analogies remain, such as the formation of light induced crossings. We show that under particular circumstances, the molecular dynamics under quantum or classical fields produce similar results, as long as the radiation is prepared as a Fock state and far from ultra-strong coupling regimes. At this point, the choice of specific initial Fock states is irrelevant since the dynamics scales. However, in realistic multistate molecular systems, radiative scaling may fail due to the presence of simultaneous efficient non-radiative couplings in the dynamics. Polar molecules have permanent dipoles, and within the context of the full quantum Rabi model with a Pauli-Fierz Hamiltonian, they play a crucial role in the polaritonic dynamics since both permanent dipole moments and self-energy terms produce drastic changes on the undressed potential energy surfaces at high coupling strengths. We also gauge the effect of including rotational degrees of freedom in cavity molecular photodynamics. For diatomic molecules, the addition of rotation amounts to transform (both with classical or quantum fields) a light induced crossing into a light induced conical intersection. However, we show that conical intersections due to molecular rotation do not represent the standard properties of well-known efficient intrinsic conical intersections inasmuch they do not enhance the quantum transition rates.
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.
A dressed-state perturbation theory beyond the rotating wave approximation(RWA) is presented to investigate the interaction between a two-level electronic transition of polar molecules and a quantized cavity field. Analytical expressions can be explicitly derived for both the ground- and excited-state-energy spectrums and wave functions of the system, where the contribution of permanent dipole moments(PDM) and the counter-rotating wave term(CRT) can be shown separately.The validity of these explicit results is discussed by comparison with the direct numerical simulation. Compared to the CRT coupling, PDM results in the coupling of more dressed states and the energy shift is proportional to the square of the normalized permanent dipole difference, and a greater Bloch–Siegert shift can be produced in the giant dipole molecule cavity QED. In addition, our method can also be extended to the solution of the two-level atom Rabi model Hamiltonian beyond the RWA.更多还原
A dressed-state perturbation theory beyond the rotating waveapproxi-mation (RWA) is presented to investigate the interaction between a two level electronic transition of the polar molecules and a quantized cavity field. Analytical expressions can be explicitly derived for both the ground- and excited-state-energy spectrums and wave functions of the system, where the contribution of permanent dipole moments (PDM) and the counter-rotating wave term (CRT) can be shown separately. The validity of these explicit results is discussed by comparing with the direct numerical simulation. Comparing to CRT coupling, PDM results in the coupling of more dressed states and the energy shift proportional to the square of the normalized permanent dipole difference, and a greater Bloch-Siegert shift could be produced in giant dipole molecule cavity QED. In addition, our method could also be extended to the solution of two-level atom Rabi model Hamiltonian beyond the RWA.
A dressed-state perturbation theory beyond the rotating wave approximation (RWA) is presented to investigate the interaction between a two level electronic transition of the polar molecules and a quantized cavity field.Analytical expressions can be explicitly derived for both the ground-and excited-state-energy spectrums and wave functions of the system, where the contribution of permanent dipole moments (PDM) and the counter-rotating wave term (CRT) can be shown separately.The validity of these explicit results is discussed by comparing with the direct numerical simulation.Comparing to CRT coupling, PDM results in the coupling of more dressed states and the energy shift proportional to the square of the normalized permanent dipole difference, and a greater Bloch-Siegert shift could be produced in giant dipole molecule cavity QED.In addition, our method could also be extended to the solution of two-level atom Rabi model Hamiltonian beyond the RWA.