• Corpus ID: 237503141

Cavity-modified unimolecular dissociation reactions via intramolecular vibrational energy redistribution

  title={Cavity-modified unimolecular dissociation reactions via intramolecular vibrational energy redistribution},
  author={Derek S. Wang and Tom'avs Neuman and Susanne F. Yelin and Johannes Flick},
Derek S. Wang, ∗ Tomáš Neuman, Susanne F. Yelin, † and Johannes Flick ‡ Harvard John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, MA 02138, USA IPCMS de Strasbourg, UMR 7504 (CNRS – Université de Strasbourg), 67034 Strasbourg, France Department of Physics, Harvard University, Cambridge, MA 02138, USA Center for Computational Quantum Physics, Flatiron Institute, New York, NY 10010, USA (Dated: September 15, 2021) 
2 Citations

Figures and Tables from this paper

A perspective on ab initio modeling of polaritonic chemistry: The role of non-equilibrium effects and quantum collectivity
non-equilibrium effects and quantum collectivity Dominik Sidler,1, 2 Michael Ruggenthaler,1, 2 Christian Schäfer,1, 2, 3, 4 Enrico Ronca,5 and Angel Rubio1, 2, 6 1)Max Planck Institute for the
Strong light-matter interaction effects on molecular ensembles
Despite the potential paradigm breaking capability of microcavities to control chemical processes, the extent to which photonic devices change properties of molecular materials is still unclear, in


Ground‐State Chemical Reactivity under Vibrational Coupling to the Vacuum Electromagnetic Field
The findings show that vibrational strong coupling provides a powerful approach for modifying and controlling chemical landscapes and for understanding reaction mechanisms.
Coherent coupling of molecular resonators with a microcavity mode
It is shown that molecular vibrational modes of the electronic ground state can also be coherently coupled with a microcavity mode at room temperature, given the low vibrational thermal occupation factors associated with molecular vibrations, and the collective coupling of a large ensemble of molecules immersed within the cavity-mode volume enables the enhancement of the collective Rabi-exchange rate with respect to the single-oscillator coupling strength.
Theory of Mode-Selective Chemistry through Polaritonic Vibrational Strong Coupling.
The theoretical results illustrate the cavity-induced mode-selective chemistry through polaritonic vibrational strong couplings, revealing the fundamental mechanism for changing chemical selectivities through cavity quantum electrodynamics.
A Roadmap Toward the Theory of Vibrational Polariton Chemistry
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
Cavity Catalysis by Cooperative Vibrational Strong Coupling of Reactant and Solvent Molecules†
The catalytic effect of vibrational strong coupling (VSC) on the solvolysis of para‐nitrophenyl acetate (PNPA), which increases the reaction rate by an order of magnitude, indicates a cooperative effect between the solvent molecules and the reactant.
Monte Carlo Calculation of Triatomic Dissociation Rates. I. N2O and O3
A very fast digital computer was used to simulate the motion of nonrotating triatomic molecules. Starting configurations were selected by a weighted random procedure which leads to correctly averaged
Resonant catalysis of thermally activated chemical reactions with vibrational polaritons
A VSC Marcus–Levich–Jortner electron transfer model is provided that potentially addresses the paradox: although entropy favors the transit through dark-state channels, the chemical kinetics can be dictated by a few polaritonic channels with smaller activation energies.
Modifying Woodward–Hoffmann Stereoselectivity Under Vibrational Strong Coupling
It is shown that VSC influences the stereoselectivity of the thermal electrocyclic ring opening of a cyclobutene derivative, a reaction which follows the Woodward–Hoffmann rules, confirming that symmetry plays a key role in chemistry under VSC.
Theory of Vibrational Polariton Chemistry in the Collective Coupling Regime
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
Coriolis-induced intramolecular vibrational energy flow between anharmonic normal modes
Abstract The classical flow of energy between anharmonic normal vibrational modes induced by Coriolis coupling is studied for a simple model of a linear triatomic molecule rotating in a plane. The