Recent experiments demonstrate polaritons under the vibrational strong coupling (VSC) regime can modify chemical reactivity. Here, we present a complete theory of VSC-modified rate constants when coupling a single molecule to an optical cavity, where the role of photonic mode lifetime is understood. The analytic expression exhibits a sharp resonance behavior, where the maximum rate constant is reached when the cavity frequency matches the vibration frequency. The theory explains why VSC rate constant modification closely resembles the optical spectra of the vibration outside the cavity. Further, we discussed the temperature dependence of the VSC-modified rate constants. The analytic theory agrees well with the numerically exact hierarchical equations of motion (HEOM) simulations for all explored regimes. Finally, we discussed the resonance condition at the normal incidence when considering in-plane momentum inside a Fabry-Pérot cavity.
We present numerically exact quantum dynamics simulations using the hierarchical equation of motion approach to investigate the resonance enhancement of chemical reactions due to the vibrational strong coupling (VSC) in polariton chemistry. The results reveal that the cavity mode acts like a “rate-promoting vibrational mode” that enhances the ground state chemical reaction rate constant when the cavity mode frequency matches the vibrational transition frequency. The exact simulation predicts that the VSC-modified rate constant will change quadratically as the light–matter coupling strength increases. When changing the cavity lifetime from the lossy limit to the lossless limit, the numerically exact results predict that there will be a turnover of the rate constant. Based on the numerical observations, we present an analytic rate theory to explain the observed sharp resonance peak of the rate profile when tuning the cavity frequency to match the quantum transition frequency of the vibrational ground state to excited states. This rate theory further explains the origin of the broadening of the rate profile. The analytic rate theory agrees with the numerical results under the golden rule limit and the short cavity lifetime limit. To the best of our knowledge, this is the first analytic theory that is able to explain the sharp resonance behavior of the VSC-modified rate profile when coupling an adiabatic ground state chemical reaction to the cavity. We envision that both the numerical analysis and the analytic theory will offer invaluable theoretical insights into the fundamental mechanism of the VSC-induced rate constant modifications in polariton chemistry.
more » « less- Award ID(s):
- 2244683
- NSF-PAR ID:
- 10502604
- Publisher / Repository:
- AIP
- Date Published:
- Journal Name:
- The Journal of Chemical Physics
- Volume:
- 159
- Issue:
- 8
- ISSN:
- 0021-9606
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
more » « less
Abstract -
more » « less
Abstract We present a theory that explains the resonance effect of the vibrational strong coupling (VSC) modified reaction rate constant at the normal incidence of a Fabry–Pérot (FP) cavity. This analytic theory is based on a mechanistic hypothesis that cavity modes promote the transition from the ground state to the vibrational excited state of the reactant, which is the rate-limiting step of the reaction. This mechanism for a single molecule coupled to a single-mode cavity has been confirmed by numerically exact simulations in our recent work in [J. Chem. Phys. 159, 084104 (2023)]. Using Fermi’s golden rule (FGR), we formulate this rate constant for many molecules coupled to many cavity modes inside a FP microcavity. The theory provides a possible explanation for the resonance condition of the observed VSC effect and a plausible explanation of why only at the normal incident angle there is the resonance effect, whereas, for an oblique incidence, there is no apparent VSC effect for the rate constant even though both cases generate Rabi splitting and forming polariton states. On the other hand, the current theory cannot explain the collective effect when a large number of molecules are collectively coupled to the cavity, and future work is required to build a complete microscopic theory to explain all observed phenomena in VSC.
-
more » « less
Abstract 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 for 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.
-
more » « less
We simulate vibrational strong coupling (VSC) and vibrational 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 H2O molecules especially under V-USC, which could play a role in ground-state chemistry.
-
Ultrafast dynamics of CN radical reactions with chloroform solvent under vibrational strong couplingmore » « less
Polariton chemistry may provide a new means to control molecular reactivity, permitting remote, reversible modification of reaction energetics, kinetics, and product yields. A considerable body of experimental and theoretical work has already demonstrated that strong coupling between a molecular vibrational mode and the confined electromagnetic field of an optical cavity can alter chemical reactivity without external illumination. However, the mechanisms underlying cavity-altered chemistry remain unclear in large part because the experimental systems examined previously are too complex for detailed analysis of their reaction dynamics. Here, we experimentally investigate photolysis-induced reactions of cyanide radicals with strongly-coupled chloroform (CHCl3) solvent molecules and examine the intracavity rates of photofragment recombination, solvent complexation, and hydrogen abstraction. We use a microfluidic optical cavity fitted with dichroic mirrors to facilitate vibrational strong coupling (VSC) of the C–H stretching mode of CHCl3 while simultaneously permitting optical access at visible wavelengths. Ultrafast transient absorption experiments performed with cavities tuned on- and off-resonance reveal that VSC of the CHCl3 C–H stretching transition does not significantly modify any measured rate constants, including those associated with the hydrogen abstraction reaction. This work represents, to the best of our knowledge, the first experimental study of an elementary bimolecular reaction under VSC. We discuss how the conspicuous absence of cavity-altered effects in this system may provide insights into the mechanisms of modified ground state reactivity under VSC and help bridge the divide between experimental results and theoretical predictions in vibrational polariton chemistry.
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1063/5.0159791
