Initialization with a Fock State Cavity Mode in Real-Time Nuclear--Electronic Orbital Polariton Dynamics

TL;DR

This study uses advanced quantum simulations to explore how initializing a cavity mode in a Fock state affects polariton dynamics, revealing phenomena that require a quantum treatment unlike classical approaches.

Contribution

It demonstrates that a Fock state initial condition leads to unique quantum phenomena in polariton dynamics, not predicted by classical or mean-field models, highlighting the importance of quantum descriptions.

Findings

Fock state initial conditions do not produce polaritons in mean-field models.

Full quantum models predict light--matter entanglement and oscillations with Fock states.

Quantum phenomena observed are not reproducible by classical electrodynamics.

Abstract

Molecular polaritons have drawn great interest in recent years as a possible avenue for providing optical control over chemical dynamics. A central challenge in the field is to identify physical phenomena that require a quantum rather than a classical treatment of electrodynamics. In this work, we use our recently developed mean-field quantum (mfq) and full-quantum (fq) real-time nuclear--electronic orbital (RT-NEO) time-dependent density functional theory methods to simulate polaritonic dynamics for a molecule under vibrational strong coupling when a quantized cavity mode is initialized in a Fock state rather than a coherent state. Our previous work showed that a coherent state initial condition for the cavity mode leads to polariton formation for both the mfq-RT-NEO and fq-RT-NEO methods. Herein, we show that the mfq-RT-NEO method, which does not allow light--matter entanglement, does not predict polariton formation for a Fock state initial condition. Similar to the mfq-RT-NEO method, the fq-RT-NEO method does not predict oscillations of the cavity mode coordinate and molecular dipole operator expectation values for a Fock state initial condition. However, the fq-RT-NEO method does predict oscillations of the expectation values of even powers of these operators as well as light--matter entanglement, implicating polariton formation with a Fock state initial condition. All these observations can be explained with model systems. These results suggest that using a quantized cavity mode initial condition that does not have a direct analogy to an initial condition in classical electrodynamics can lead to physical phenomena that can only be described by a quantum treatment of the cavity mode.