Nuclear-Electronic Orbital Theory for Polaritons and Plasmons
Abstract
A longstanding goal of polaritonic and plasmonic chemistry is to control chemical reactions through electromagnetic fields. Molecular polaritons are hybrid light-matter states arising from strong coupling between cavity modes and molecular electronic or vibrational transitions. Surface plasmon resonances are coherent localized oscillations of electrons within metal nanoparticles induced by photoexcitation. The potential of molecular polaritons and surface plasmons for influencing energy transfer, chemical synthesis, and catalysis, as well as optoelectronic and photonic devices, is of interest to the Air Force. The objective of this proposal is to develop theoretical approaches for simulating the nuclear-electronic quantum dynamics of polaritonic and plasmonic systems to elucidate the mechanisms by which they can control chemical reactivity. These approaches will be based on the real-time nuclear-electronic orbitalmethods, which treat all electrons and specified protons quantum mechanically on the same level. This framework enables the investigation of both electronic and vibrational strong coupling in polaritonic systems, as well as both electronic and infrared resonance in surface plasmonic systems. A variety of strategies for describing collective polaritonic effects on proton transfer and proton-coupled electron transfer reactions in cavities, as well as plasmonic electron and energy transfer in nanostructures, will be explored. The resulting insights will be important for designing more effective energy conversion and energy transport systems, as well as more efficient photocatalytic processes.
Document Details
- Document Type
- DoD Grant Award
- Publication Date
- Feb 06, 2025
- Source ID
- FA95502410347
Entities
People
- Sharon Hammes-Schiffer
Organizations
- Air Force Office of Scientific Research
- Trustees of Princeton University
- United States Air Force