Molecular dynamics study of plasmon-mediated chemical transformations

Abstract

Heterogeneous catalysis of adsorbates on metallic surfaces mediated by plasmon has potential high photoelectric conversion efficiency and controllable reaction selectivity. Theoretical modeling of dynamical reaction processes provides in-depth analyses complementing...

Theory and modeling of light-matter interactions in chemistry: current and future

“…This leads to an emerging field of plasmon chemistry that designs nanostructure-based surface plasmons as mediators to redistribute and convert photon energy in various time, space, and energy scales to drive chemical reactions. 20–22,92,106–116 One extraordinary feature of Plasmon chemistry in the realm of chemical reaction mechanisms is its blend of facets from thermochemistry, photochemistry, and photocatalysis. 92 Unlike traditional reactions that typically focus on singular mechanisms, plasmon chemistry showcases the interaction between different mechanisms in complex electronic and optical environments.…”

“…Even for a small nanoparticle (2 nm diameter, for example), thousands of excited states are to be computed to reach the plasmon excitations. 108…”

“…The NEXMD-DFTB method was employed to investigate the plasmon-induced bond activation of CO adsorbed on Au 20 cluster. 108 The simulations provide a comprehensive and accurate depiction of the multiple dynamic processes involved in plasmon-mediated chemistry, including plasmon excitation, HEs relaxation, direct/indirect HE transfer, and the activation of CO vibration mode induced by HE transfers. These simulations reveal the critical role of charge transfer (CT) states in plasmon-induced CO activation.…”

Nuclear-Electronic Orbital Quantum Dynamics of Plasmon-Driven H2 Photodissociation

“…Although this approximation is valid for describing the initial photodissociation dynamics of this system (Figure S3), simulations at longer time scales should include the dynamics of the metal atoms to ensure quantitative accuracy. 36 The RT-NEO-TDDFT approach was implemented 37 in a developer version of Q-Chem. 38 See the Supporting Information (SI) for more simulation details, including validation of the TPB approach and calculations with larger electronic basis sets and a different electronic functional.…”

“…The Al atoms were fixed during all NEO and conventional simulations. Although this approximation is valid for describing the initial photodissociation dynamics of this system (Figure S3), simulations at longer time scales should include the dynamics of the metal atoms to ensure quantitative accuracy . The RT-NEO-TDDFT approach was implemented in a developer version of Q-Chem .…”