The Shape of the Electric Dipole Function Determines the Sub-Picosecond Dynamics of Anharmonic Vibrational Polaritons

Abstract

We develop a fully quantum mechanical methodology to describe the static properties and the dynamics of a single anharmonic vibrational mode interacting with a quantized infrared cavity field in the strong and ultrastrong coupling regimes. By comparing multiconfiguration time-dependent Hartree (MCTDH) simulations for a Morse oscillator in a cavity, with an equivalent formulation of the problem in Hilbert space, we describe for the first time the essential role of permanent dipole moments in the femtosecond dynamics of vibrational polariton wavepackets. We show that depending on the shape of the electric dipole function $d_e(q)$ along the vibrational mode coordinate $q$, molecules can be classified into three general families. For molecules that are polar and have a positive slope of the dipole function at equilibrium, we show that an initial diabatic light-matter product state without vibrational or cavity excitations can evolve into a polariton wavepacket with a large number of intracavity photons, for interaction strengths at the onset of ultrastrong coupling. This build up of intracavity photon amplitude is accompanied by an effective $lengthening$ of the vibrational mode of nearly $10\%$, comparable with a laser-induced vibrational excitation in free space. In contrast, molecules that are also polar at equilibrium but have a negative slope of the dipole function, experience an effective mode $shortening$ under equivalent coupling conditions. Our model predictions are numerically validated using realistic $ab$-$initio$ potentials and dipole functions for HF and CO${}_2$ molecules in their ground electronic states. We finally propose a non-adiabatic state preparation scheme to generate vibrational polaritons using nanoscale infrared antennas and UV-vis photochemistry or electron tunneling, to enable the far-field detection of spontaneously generated infrared quantum light.

arXiv comment16 pages, 10 figures, 57 refs

References in corpus (26)

• Ultrastrong coupling between light and matter
• Ultrastrong coupling regimes of light-matter interaction
• On the Integrability of the Rabi Model
• Coherent coupling of molecular resonators with a micro-cavity mode
• Introduction to the Dicke model: from equilibrium to nonequilibrium, and vice versa
• Molecular polaritons for controlling chemistry with quantum optics
• Multiple Rabi Splittings under Ultra-Strong Vibrational Coupling
• Resonant catalysis of thermally-activated chemical reactions via vibrational polaritons
• Quantum theory of collective strong coupling of molecular vibrations with a microcavity mode
• Cavity Casimir-Polder forces and their effects in ground state chemical reactivity
• Spontaneous Conversion from Virtual to Real Photons in the Ultrastrong Coupling Regime
• Non-adiabatic dynamics of molecules in optical cavities
• Absorption and Photoluminescence in Organic Cavity QED
• Can ultrastrong coupling change ground state chemical reactions?
• Rabi model beyond the rotating wave approximation: generation of photons from vacuum through decoherence
• Perspective: Quantum Hamiltonians for Optical Interactions
• Dissipation and Thermal Noise in Hybrid Quantum Systems in the Ultrastrong Coupling Regime
• Strong coupling in the far-infrared between graphene plasmons and the surface optical phonons of silicon dioxide
• Signatures of Vibrational Strong Coupling in Raman Scattering
• Two-dimensional Infrared Spectroscopy of vibrational polaritons of molecules in an optical cavity
• Multi-level quantum Rabi model for anharmonic vibrational polaritons
• Entangled Photonic-Nuclear Molecular Dynamics of LiF in Quantum Optical Cavities
• Ultrafast dynamics in the vicinity of quantum light-induced conical intersections
• Dynamical correlation functions and the quantum Rabi model
• Raman scattering with strongly coupled vibron-polaritons
• Dipolar and Quadrupolar Excitons Coupled to a Nanoparticle-on-a-Mirror Cavity

Cited by in corpus (21)

• Swinging between shine and shadow: Theoretical advances on thermally-activated vibropolaritonic chemistry (a perspective)
• Resonant Cavity Modification of Ground State Chemical Kinetics
• Polariton relaxation under vibrational strong coupling: Comparing cavity molecular dynamics simulations against Fermi's golden rule rate
• Cavity-Altered Thermal Isomerization Rates and Dynamical Resonant Localization in Vibro-Polaritonic Chemistry
• Energy-efficient pathway for selectively exciting solute molecules to high vibrational states via solvent vibration-polariton pumping
• Generalization of the Tavis-Cummings model for multi-level anharmonic systems: insights on the second excitation manifold
• QM/MM Modeling of Vibrational Polariton Induced Energy Transfer and Chemical Dynamics
• Semiclassical Real-Time Nuclear-Electronic Orbital Dynamics for Molecular Polaritons: Unified Theory of Electronic and Vibrational Strong Couplings
• Chemical reactivity under collective vibrational strong coupling
• Generalization of the Tavis-Cummings model for multi-level anharmonic systems
• Dissociation dynamics of a diatomic molecule in an optical cavity
• Vibropolaritonic Reaction Rates in the Collective Strong Coupling Regime: Pollak-Grabert-Hänggi Theory
• Nonadiabatic phenomena in molecular vibrational polaritons
• An efficient and flexible approach for computing rovibrational polaritons from first principles
• Semi-empirical Quantum Optics for Mid-Infrared Molecular Nanophotonics
• Selective Excitation of IR-Inactive Modes via Vibrational Polaritons: Insights from Atomistic Simulations
• Open quantum dynamics of strongly coupled oscillators with multi-configuration time-dependent Hartree propagation and Markovian quantum jumps
• Ab initio study on the dynamics and spectroscopy of collective rovibrational polaritons
• Model for vibrationally enhanced tunneling of proton transfer in hydrogen bond
• Schrödinger equation with Pauli-Fierz Hamiltonian and double well potential as model of vibrationally enhanced tunneling for proton transfer in hydrogen bond
• Semiclassical Dynamics in Wigner Phase Space I : Adiabatic Hybrid Wigner Dynamics