We simulate vibrational strong (VSC) and ultrastrong coupling (V-USC) for liquid water with classical molecular dynamics simulations. When the cavity modes are resonantly coupled to the O-H stretch mode of liquid water, the infrared spectrum shows asymmetric Rabi splitting. The lower polariton (LP) may be suppressed or enhanced relative to the upper polariton (UP) depending on the frequency of the cavity mode. Moreover, although the static properties and the translational diffusion of water are not changed under VSC or V-USC, we do find the modification of the orientational autocorrelation function of H$_2$O molecules especially under V-USC, which could play a role in ground-state chemistry.
Recent experiments and theory demonstrate that the the ground state properties and chemical reactivity of molecules can be modified inside an optical cavity. The vibrational strong or ultrastrong coupling results in the formation of vibrational polaritons which are usually observed through infrared spectra (IR). Here, we provide a theoretical framework to conduct multidimensional quantum simulations of the infrared spectra when the molecule is interacting with cavity modes. Taking single water molecule as an example, combing with accurate potential energy and dipole moment surfaces, our implem…
Recent experiments showed that the chemical reaction rate is modified, either increased or decreased, by strongly coupling a nuclear vibration mode to the single mode of an optical cavity. Herein we investigate how the rate of an electron-transfer reaction depends on the molecule-cavity coupling in the ultrastrong coupling regime, where the coupling strength is comparable in magnitude with both the vibrational and the cavity frequencies. We found two main factors that determine the modification of the reaction rate: the relative shifts of the energy levels induced by the coupling and the mixin…
The strong coupling of an IR-active molecular transition with an optical mode of the cavity results in vibrational polaritons, which opens a new way to control chemical reactivity via confined electromagnetic fields of the cavity. In this study, we design a voltage-tunable open microcavity and we show the formation of multiple vibrational polaritons in methyl salicylate. A Rabi splitting and polariton anticrossing behaviour is observed when the cavity mode hybridizes with the C=O stretching vibration of methyl salicylate. As this vibration contributes to the reaction coordinate of the photoind…
For a small fraction of hot CO2 molecules immersed in a liquid-phase CO2 thermal bath, classical cavity molecular dynamics simulations show that forming collective vibrational strong coupling (VSC) between the C=O asymmetric stretch of CO2 molecules and a cavity mode accelerates hot-molecule relaxation. The physical mechanism underlying this acceleration is the fact that polaritons, especially the lower polariton, can be transiently excited during the nonequilibrium process, which facilitates intermolecular vibrational energy transfer. The VSC effects on these rates (i) resonantly depend on th…
Selectively exciting target molecules to high vibrational states is inefficient in the liquid phase, which restricts the use of IR pumping to catalyze ground-state chemical reactions. Here, we demonstrate that this inefficiency can sometimes be solved by confining the liquid to an optical cavity under vibrational strong coupling conditions. For a liquid solution of 13CO2 solute in a 12CO2 solvent, cavity molecular dynamics simulations show that exciting a polariton (hybrid light-matter state) of the solvent with an intense laser pulse, under suitable resonant conditions, may lead to a very str…
Recent experiments have observed that the chemical and photophysical properties of molecules can be modified inside an optical Fabry-Perot microcavity under collective vibrational strong coupling (VSC) conditions, and such modification is currently not well understood by theory. In an effort to understand the origin of such cavity induced phenomena, some recent studies have focused on the effect of the cavity environment on the nonlinear optical response of the molecular subsystem. Here, we use a recently proposed protocol for classical cavity molecular dynamics (CavMD) simulations to numerica…
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 th…
While the emerging field of vibrational polariton chemistry has the potential to overcome traditional limitations of synthetic chemistry, the underlying mechanism is not yet well understood. Here, we explore how the dynamics of unimolecular dissociation reactions that are rate-limited by intramolecular vibrational energy redistribution (IVR) can be modified inside an infrared optical cavity. We study a classical model of a bent triatomic molecule, where the two outer atoms are bound by anharmonic Morse potentials to the center atom coupled to a harmonic bending mode. We show that an optical ca…
We report Doppler-free two-photon absorption of N$_2$O at $λ$ = 4.53 $μ$m, measured by cavity ring-down spectroscopy. High power was achieved by optical self-locking of a quantum cascade laser to a linear resonator of finesse $F$ = 22730, and accurate laser detuning over a 400 MHz range was measured relative to an optical frequency comb. At a sample pressure of p = 0.13 kPa, we report a large two-photon cross-section of $σ_{13}^{(2)}$ = 8.0 $\times$ 10$^{-41}$ cm$^4$ s molecule$^{-1}$ for the $Q$(18) rovibrational transition at a resonant frequency of $ν_0$ = 66179400.8 MHz.
A novel mid-infrared/near-infrared double resonant absorption setup for studying infrared-inactive vibrational states is presented. A strong vibrational transition in the mid-infrared region is excited using an idler beam from a singly resonant continuous-wave optical parametric oscillator, to populate an intermediate vibrational state. High output power of the optical parametric oscillator and the strength of the mid-infrared transition result in efficient population transfer to the intermediate state, which allows measuring secondary transitions from this state with a high signal-to-noise ra…
We theoretically demonstrate that chemical reaction rate constant can be significantly suppressed by coupling molecular vibrations with an optical cavity, exhibiting both the collective coupling effect and the cavity-frequency modification of the rate constant. When a reaction coordinate is strongly coupled to the solvent molecules, the reaction rate constant is reduced due to the dynamical caging effect. We demonstrate that collectively coupling the solvent to the cavity can further enhance this dynamical caging effect, leading to additional suppression of the chemical kinetics. This effect i…
The electromagnetic field in an optical cavity can dramatically modify and even control chemical reactivity via vibrational strong coupling (VSC). Since the typical vibration and cavity frequencies are considerably higher than thermal energy, it is essential to adopt a quantum description of cavity-catalyzed adiabatic chemical reactions. Using quantum transition state theory (TST), we examine the coherent nature of adiabatic reactions and derive the cavity-induced changes in eigen frequencies, zero-point-energy, and quantum tunneling. The resulting quantum TST calculation allows us to explain …
Interaction between light and molecular vibrations leads to hybrid light-matter states called vibrational polaritons. Even though many intriguing phenomena have been predicted for single-molecule vibrational strong coupling (VSC), several studies suggest that these effects tend to be diminished in the many-molecule regime due to the presence of dark states. Achieving single or few-molecule vibrational polaritons has been constrained by the need for fabricating extremely small mode volume infrared cavities. In this work, we propose an alternative strategy to achieve single-molecule VSC in a cav…
The field of vibrational polariton chemistry was firmly established in 2016 when a chemical reaction rate at room temperature was modified within a resonantly tuned infrared cavity without externally driving the system. Despite intense efforts by scientists around the world to understand why the reaction rate changes, no convincing theoretical explanation exists. In this perspective, first, we briefly review this seminal experiment, as well as relevant experiments that have since followed that have hinted at the roles of reactant concentration, cavity frequency, and symmetry. Then, we analyze …
Cavity-modified electronic interactions in molecular ensembles under vibrational strong coupling: Combined insights from cavity Born-Oppenheimer perturbation and ab initio wave function theories
We propose a cavity QED approach to describe light-matter interaction between an individual anharmonic molecular vibration and an infrared cavity field. Starting from a generic Morse oscillator with quantized nuclear motion, we derive a multi-level quantum Rabi model to study vibrational polaritons beyond the rotating-wave approximation. We analyze the spectrum of vibrational polaritons in detail and compare with available experiments. For high excitation energies, the spectrum exhibits a dense manifold of true and avoided level crossings as the light-matter coupling strength and cavity freque…
Under vibrational strong coupling (VSC), the formation of molecular polaritons may significantly modify the photo-induced or thermal properties of molecules. In an effort to understand these intriguing modifications, both experimental and theoretical studies have focused on the ultrafast dynamics of vibrational polaritons. Here, following our recent work [J. Chem. Phys., 154, 094124, (2021)], we systematically study the mechanism of polariton relaxation for liquid CO2 under a weak external pumping. Classical cavity molecular dynamics (CavMD) simulations show that polariton relaxation results f…
The demonstration of strong and ultrastrong coupling regimes of cavity QED with polyatomic molecules has opened new routes to control chemical dynamics at the nanoscale. We show that strong resonant coupling of a cavity field with an electronic transition can effectively decouple collective electronic and nuclear degrees of freedom in a disordered molecular ensemble, even for molecules with high-frequency quantum vibrational modes having strong electron-vibration interactions. This type of polaron decoupling can be used to control chemical reactions. We show that the rate of electron transfer …
Controlling the quantum field statistics of confined light is a long-standing goal in integrated photonics. We show that by coupling molecular vibrations with a confined mid-infrared cavity vacuum, the photocount and quadrature field statistics of the cavity field can be reversibly manipulated over sub-picosecond timescales. The mechanism involves changing the cavity resonance frequency through a modulation of the dielectric response of the cavity materials using femtosecond UV pulses. For a single anharmonic molecular vibration in an infrared cavity under ultrastrong coupling conditions, the …
Recent experiments of chemical reactions in optical cavities have shown great promise to alter and steer chemical reactions but still remain poorly understood theoretically. In particular the origin of resonant effects between the cavity and certain vibrational modes in the collective limit is still subject to active research. In this paper, we study unimolecular dissociation reactions of many molecules collectively interacting with an infrared cavity mode through their vibrational dipole moment. We find that the reaction rate can slow down by increasing the number of aligned molecules if the …
