Speaker
Description
The observed modification of thermal chemical rates in Fabry-Perot cavities
remains poorly understood. Mounting evidence supported by theory indicates that
the cavity has a small effect on the potential energy barrier, suggesting that
dynamical corrections may play a prominent role. This is in line with the
relatively small modifications of the rate constant usually reported, often not
exceeding a factor of 10, at most.
Here we will describe classical atomistic simulations on an ab initio potential
of the cis-trans isomerization reaction of nitrous oxide (HONO) in a cavity [1].
Using the flux method to compute the recrossing coefficient, we will examine the
conditions under which the cavity induces modifications of the reactive flux
leading to modifications of the thermal rate. We will also consider small
ensembles of HONO molecules in the gas phase, and thus shed light on the role of
collective effects through specific numerical experiments [2].
Switching gears, and if time permits, I will introduce a few hints on the role
of molecular symmetry and Jahn-Teller distortions in optical cavities, and how
vibronic effects can result in exotic "inverse polarization" states.
References:
[1] Sun, Vendrell; JPCL 13, 4441 (2022)
[2] Sun, Vendrell; JPCL 14, 8397 (2023)
[3] Nandipati, Vendrell; PRA 107, L061101 (2023)
