Molecular photodissociation enabled by ultrafast plasmon decay

TL;DR

This paper introduces a method to induce photodissociation in stable molecules by coupling them with plasmonic nanoparticles, utilizing ultrafast plasmon decay to transfer energy and break molecular bonds.

Contribution

It presents a novel approach to enable molecular photodissociation through plasmon coupling and demonstrates it with numerical simulations of hydrogen near aluminum nanoparticles.

Findings

Efficient photodissociation can be achieved via ultrafast plasmon decay.

The process involves a Raman-like energy transfer to the molecule.

Simulation results show dependence on system parameters.

Abstract

We propose a strategy for enabling photodissociation of a normally photostable molecule through coupling to a nanoparticle plasmon. The large possible coupling on the single-molecule level combined with the highly lossy nature of plasmonic modes, with lifetimes on the order of femtoseconds, opens an ultrafast decay channel for the molecule. For plasmon mode frequencies below the vertical photoexcitation energy of the molecule, the difference between excitation and emission energy is converted into vibrational energy on the molecular ground state in a Raman-like process. Under the correct conditions, this energy can be high enough to enable efficient photodissociation on the electronic ground state. We demonstrate the concept using numerical simulations of the Lindblad master equation for the hydrogen molecule in the vicinity of an aluminum nanoparticle, and explore the photodissociation efficiency as a function of various system parameters.