Cavity-Altered Thermal Isomerization Rates and Dynamical Resonant
Localization in Vibro-Polaritonic Chemistry
- URL: http://arxiv.org/abs/2109.13574v3
- Date: Thu, 4 Nov 2021 10:23:21 GMT
- Title: Cavity-Altered Thermal Isomerization Rates and Dynamical Resonant
Localization in Vibro-Polaritonic Chemistry
- Authors: Eric W. Fischer, Janet Anders, Peter Saalfrank
- Abstract summary: Reaction rates for molecules embedded in microfluidic optical cavities are altered when compared to rates observed under "ordinary" reaction conditions.
We study how strong coupling of an optical cavity mode to molecular vibrations affect the reactivity and how resonance behavior emerges.
- Score: 0.0
- License: http://creativecommons.org/licenses/by/4.0/
- Abstract: It has been experimentally demonstrated that reaction rates for molecules
embedded in microfluidic optical cavities are altered when compared to rates
observed under "ordinary" reaction conditions. However, precise mechanisms of
how strong coupling of an optical cavity mode to molecular vibrations affect
the reactivity and how resonance behavior emerges are still under dispute. In
the present work, we approach these mechanistic issues from the perspective of
a thermal model reaction, the inversion of ammonia along the umbrella mode, in
presence of a single cavity mode of varying frequency and coupling strength. A
topological analysis of the related cavity Born-Oppenheimer potential energy
surface in combination with quantum mechanical and transition state theory rate
calculations reveals two quantum effects, leading to decelerated reaction rates
in qualitative agreement with experiments: The stiffening of quantized modes
perpendicular to the reaction path at the transition state, which reduces the
number of thermally accessible reaction channels, and the broadening of the
barrier region which attenuates tunneling. We find these two effects to be very
robust in a fluctuating environment, causing statistical variations of
potential parameters such as the barrier height. Further, by solving the
time-dependent Schr\"odinger equation in the vibrational strong coupling
regime, we identify a resonance behavior, in qualitative agreement with
experimental and earlier theoretical work. The latter manifests as reduced
reaction probability, when the cavity frequency $\omega_c$ is tuned resonant to
a molecular reactant frequency. We find this effect to be based on the
dynamical localization of the vibro-polaritonic wavepacket in the reactant
well.
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