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We derive the $\mathcal{L}$-MFE method to incorporate Lindblad jump operator dynamics into the mean-field Ehrenfest (MFE) approach. We map the density matrix evolution of Lindblad dynamics onto pure state coefficients using trajectory averages. We use simple assumptions to construct the $\mathcal{L}$-MFE method that satisfies this exact mapping. This establishes a method that uses independent trajectories which exactly reproduces Lindblad decay dynamics using a wavefunction description, with deterministic changes of the magnitudes of the quantum expansion coefficients, while only adding on a stochastic phase. We further demonstrate that when including nuclei in the Ehrenfest dynamics, the $\mathcal{L}$-MFE method gives semi-quantitatively accuratemore »results, with the accuracy limited by the accuracy of the approximations present in the semiclassical MFE approach. This work provides a general framework to incorporate Lindblad dynamics into semiclassical or mixed quantum-classical simulations.« less

This work provides the fundamental theoretical framework for few-mode cavity quantum electrodynamics by resolving the gauge ambiguities between the Coulomb gauge and the dipole gauge Hamiltonians under the photonic mode truncation. We first propose a general framework to resolve ambiguities for an arbitrary truncation in a given gauge. Then, we specifically consider the case of mode truncation, deriving gauge invariant expressions for both the Coulomb and dipole gauge Hamiltonians that naturally reduce to the commonly used single-mode Hamiltonians when considering a single-mode truncation. We finally provide the analytical and numerical results of both atomic and molecular model systems coupled tomore »the cavity to demonstrate the validity of our theory.« less

We investigate the Polariton induced conical intersection (PICI) created from coupling a diatomic molecule with the quantized photon mode inside an optical cavity, and the corresponding Berry Phase effects. We use the rigorous Pauli–Fierz Hamiltonian to describe the quantum light-matter interactions between a LiF molecule and the cavity, and use the exact quantum propagation to investigate the polariton quantum dynamics. The molecular rotations relative to the cavity polarization direction play a role as the tuning mode of the PICI, resulting in an effective CI even within a diatomic molecule. To clearly demonstrate the dynamical effects of the Berry phase, wemore »construct two additional models that have the same Born–Oppenheimer surface, but the effects of the geometric phase are removed. We find that when the initial wavefunction is placed in the lower polaritonic surface, the Berry phase causes a π phase-shift in the wavefunction after the encirclement around the CI, indicated from the nuclear probability distribution. On the other hand, when the initial wavefunction is placed in the upper polaritonic surface, the geometric phase significantly influences the couplings between polaritonic states and therefore, the population dynamics between them. These BP effects are further demonstrated through the photo-fragment angular distribution. PICI created from the quantized radiation field has the promise to open up new possibilities to modulate photochemical reactivities.« less

Recent experiments demonstrate the control of chemical reactivities by coupling molecules inside an optical microcavity. In contrast, transition state theory predicts no change of the reaction barrier height during this process. Here, we present a theoretical explanation of the cavity modification of the ground state reactivity in the vibrational strong coupling (VSC) regime in polariton chemistry. Our theoretical results suggest that the VSC kinetics modification is originated from the non-Markovian dynamics of the cavity radiation mode that couples to the molecule, leading to the dynamical caging effect of the reaction coordinate and the suppression of reaction rate constant formore »a specific range of photon frequency close to the barrier frequency. We use a simple analytical non-Markovian rate theory to describe a single molecular system coupled to a cavity mode. We demonstrate the accuracy of the rate theory by performing direct numerical calculations of the transmission coefficients with the same model of the molecule-cavity hybrid system. Our simulations and analytical theory provide a plausible explanation of the photon frequency dependent modification of the chemical reactivities in the VSC polariton chemistry.

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