Time-dependent Kohn-Sham electron dynamics coupled with nonequilibrium plasmonic response via atomistic...

Area of Science:

• Computational Chemistry
• Materials Science
• Physical Chemistry

Background:

• Accurate computational modeling of plasmon-molecule interactions is crucial for understanding and designing nanostructures.
• Existing methods face challenges in efficiently simulating coupled plasmon-molecule systems.
• Plasmon-mediated effects significantly influence molecular properties and reactivity.

Purpose of the Study:

• To present a novel hybrid computational scheme for simulating plasmon-molecule systems.
• To enable accurate and efficient real-time simulations of plasmon-mediated electronic and nuclear dynamics.
• To investigate plasmon-enhanced molecular behavior and the influence of nanostructure design.

Main Methods:

• Developed a time-domain formulation of the fluctuating charge (TD-ωFQ) model from its frequency-domain counterpart.
• Integrated the TD-ωFQ model with the real-time time-dependent density functional theory (RT-TDDFT) approach.
• Applied the combined RT-TDDFT/TD-ωFQ scheme to study molecular systems near plasmonic metal nanoparticles (PMNPs).

Main Results:

• The RT-TDDFT/TD-ωFQ scheme successfully simulates real-time electronic dynamics in coupled plasmon-molecule systems.
• Calculated nonradiative decay rates and plasmon-enhanced absorption spectra for molecules near sodium nanoparticles.
• Revealed the impact of nanoparticle edge effects on absorption enhancement due to the atomistic nature of the ωFQ model.

Conclusions:

• The RT-TDDFT/TD-ωFQ hybrid method provides an accurate and efficient protocol for simulating plasmon-molecule interactions.
• This method advances the understanding of plasmon-enhanced photophysical and photochemical processes.
• The approach facilitates the rational design and control of nanostructures for tailored molecular properties.