First-Principles Insights into Plasmon-Induced Catalysis

• Published in: Annual review of physical chemistry Vol. 72; no. 1; pp. 99 - 119
• Main Authors: Martirez, John Mark P, Bao, Junwei Lucas, Carter, Emily A
• Format: Journal Article
• Language: English
• Published: United States Annual Reviews 20.04.2021; Annual Reviews, Inc
• Subjects: Catalysis; Chemical reactions; correlated wavefunction methods; Density functional theory; Electric fields; Electromagnetic absorption; embedding methods; First principles; heterogeneous catalysis; Nanoparticles; photocatalysis; plasmonic catalysis; Plasmonics; Quantum mechanics; Reaction kinetics; Wave functions; correlated wavefunction methods; embedding methods; plasmonic catalysis; heterogeneous catalysis; photocatalysis; density functional theory
• ISSN: 0066-426X; 1545-1593
• DOI: 10.1146/annurev-physchem-061020-053501

The size- and shape-controlled enhanced optical response of metal nanoparticles (NPs) is referred to as a localized surface plasmon resonance (LSPR). LSPRs result in amplified surface and interparticle electric fields, which then enhance light absorption of the molecules or other materials coupled to the metallic NPs and or generate hot carriers within the NPs themselves. When mediated by metallic NPs, photocatalysis can take advantage of this unique optical phenomenon. This review highlights the contributions of quantum mechanical modeling in understanding and guiding current attempts to incorporate plasmonic excitations to improve the kinetics of heterogeneously catalyzed reactions. A range of first-principles quantum mechanics techniques has offered insights, from ground-state density functional theory (DFT) to excited-state theories such as multireference correlated wavefunction methods. Here we discuss the advantages and limitations of these methods in the context of accurately capturing plasmonic effects, with accompanying examples.