Energy-efficient pathway for selectively exciting solute molecules to high vibrational states via solvent vibration-polariton pumping

@article{Li2022EnergyefficientPF,
  title={Energy-efficient pathway for selectively exciting solute molecules to high vibrational states via solvent vibration-polariton pumping},
  author={Tao E. Li and Abraham Nitzan and Joseph E Subotnik},
  journal={Nature Communications},
  year={2022},
  volume={13}
}
Selectively exciting target molecules to high vibrational states is inefficient in the liquid phase, which restricts the use of IR pumping to catalyze ground-state chemical reactions. Here, we demonstrate that this inefficiency can sometimes be solved by confining the liquid to an optical cavity under vibrational strong coupling conditions. For a liquid solution of 13CO2 solute in a 12CO2 solvent, cavity molecular dynamics simulations show that exciting a polariton (hybrid light-matter state… 
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References

SHOWING 1-10 OF 70 REFERENCES

Intermolecular vibrational energy transfer enabled by microcavity strong light–matter coupling

Using pump-probe and two-dimensional infrared spectroscopy, it is found that the excitation of the upper polariton can efficiently relax to the acceptors within ~5 picoseconds, suggesting that the energy transfer is a polaritonic process.

Cavity molecular dynamics simulations of liquid water under vibrational ultrastrong coupling

A simulation tool for modeling vibrational strong coupling and vibrational ultrastrong coupling at the interface between optics, chemistry, and biology is developed and reveals an asymmetric Rabi splitting in the infrared spectrum, but also captures cavity modification of the dynamic properties of water.

Reproducibility of cavity-enhanced chemical reaction rates in the vibrational strong coupling regime.

An attempt to reproduce the enhanced rate of cyanate ion hydrolysis reported by Hiura et al. using a piezo-tunable microcavity but fails to observe any change in the reaction rate as the cavity thickness is tuned in and out of the strong coupling regime during a given experiment.

Collective vibrational strong coupling effects on molecular vibrational relaxation and energy transfer: Numerical insights via cavity molecular dynamics simulations.

As far as the parameter dependence is concerned, the vibrational relaxation data presented here appears analogous to VSC catalysis in Fabry-Pérot microcavities.

State-Selective Polariton to Dark State Relaxation Dynamics.

This work studies the dynamics of molecular vibrational polaritons in various solvent environments and proposes the intermediate state to be the high-lying excited states of dark modes, which are effectively populated by LP via, e.g., ladder-climbing.

Cavity molecular dynamics simulations of vibrational polariton-enhanced molecular nonlinear absorption.

A recently proposed protocol for classical cavity molecular dynamics simulations is used to numerically investigate the linear and the nonlinear response of liquid carbon dioxide under collective vibrational strong coupling conditions following an optical pulse excitation and finds that applying a strong pulse of excitation to the lower polariton can lead to an overall molecular nonlinear absorption.

Toward control of electron transfer in donor-acceptor molecules by bond-specific infrared excitation

It is demonstrated how the outcome of light-induced ET can be radically altered by mode-specific infrared (IR) excitation of vibrations that are coupled to the ET pathway, effectively switching a charge separation pathway off.

Excited-state vibration-polariton transitions and dynamics in nitroprusside

Spectroscopy and dynamics of cavity coupled NO band of sodium nitroprusside are reported using 2D infrared and transient spectroscopy employing pump-probe technique and signatures of third-order nonlinearity, incoherent and strong coupling effects of vibrational polaritons are found.

Molecular vibrational polariton: Its dynamics and potentials in novel chemistry and quantum technology.

These recent works show that molecular vibrational polaritons can have distinct dynamics from its pure molecular counterparts, such as intermolecular vibrational energy transfer and hot vibrational dynamics.

IR laser excitation controlled reaction acceleration in the electronic ground state.

The acceleration of a bimolecular alcoholysis reaction is described as a paradigm for IR light driven ground state reactions and strategies to use vibrational energy relaxation pathways to single out vibrations belonging to the RC are examined.
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