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Molecular isomerization rates are modified by optical cavities. This study shows virtual photons can enhance or suppress isomerization, with classical and quantum models showing agreement. Dark cavities suppress isomerization, with poor classical-quantum correspondence.

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Area of Science:

  • Chemical Physics
  • Quantum Optics
  • Molecular Dynamics

Background:

  • Optical cavities can alter chemical reaction mechanisms.
  • Cavity-mediated changes in molecular vibrational energy flow are significant.
  • Understanding polaritonic systems is key to controlling reactions.

Purpose of the Study:

  • To investigate how optical cavities influence molecular isomerization.
  • To analyze a model polaritonic system with one-dimensional isomerization coupled to a photon mode.
  • To explore the role of virtual and zero photons in reaction dynamics.

Main Methods:

  • Studied a model polaritonic system (isomerization mode coupled to a photon mode).
  • Analyzed isomerization probability with varying cavity-system coupling and frequencies.
  • Compared classical and quantum average isomerization probabilities.

Main Results:

  • Virtual photons can suppress or enhance isomerization based on initial conditions and cavity parameters.
  • Classical and quantum models show qualitative agreement for virtual photon cases.
  • Dark cavities suppress isomerization near the fundamental frequency, with poor classical-quantum correspondence.

Conclusions:

  • Cavity effects on isomerization involve "chaos-order-chaos" transitions and polariton state localization.
  • Isomerization suppression/enhancement results from energy flow dynamics and quantum tunneling.
  • Classical-quantum correspondence varies significantly with photon presence.