Can ultrastrong coupling change ground state chemical reactions?
Autor: | Jorge A. Campos-Gonzalez-Angulo, Luis A. Martínez-Martínez, Raphael F. Ribeiro, Joel Yuen-Zhou |
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Rok vydání: | 2017 |
Předmět: |
Work (thermodynamics)
Field (physics) FOS: Physical sciences 02 engineering and technology 01 natural sciences Chemical thermodynamics Physics - Chemical Physics 0103 physical sciences Mesoscale and Nanoscale Physics (cond-mat.mes-hall) Molecule Electrical and Electronic Engineering 010306 general physics Chemical Physics (physics.chem-ph) Condensed Matter - Materials Science Condensed Matter - Mesoscale and Nanoscale Physics Energy landscape Materials Science (cond-mat.mtrl-sci) 021001 nanoscience & nanotechnology Atomic and Molecular Physics and Optics Electronic Optical and Magnetic Materials Chemical physics Excited state Potential energy surface 0210 nano-technology Ground state Biotechnology |
DOI: | 10.48550/arxiv.1705.10655 |
Popis: | Recent advancements on the fabrication of organic micro- and nanostructures have permitted the strong collective light-matter coupling regime to be reached with molecular materials. Pioneering works in this direction have shown the effects of this regime in the excited state reactivity of molecular systems and at the same time has opened up the question of whether it is possible to introduce any modifications in the electronic ground energy landscape which could affect chemical thermodynamics and/or kinetics. In this work, we use a model system of many molecules coupled to a surface-plasmon field to gain insight on the key parameters which govern the modifications of the ground-state Potential Energy Surface (PES). Our findings confirm that the energetic changes per molecule are determined by single-molecule-light couplings which are essentially local, in contrast with those of the electronically excited states, for which energetic corrections are of a collective nature. Still, we reveal some intriguing quantum-coherent effects associated with pathways of concerted reactions, where two or more molecules undergo reactions simultaneously, and which can be of relevance in low-barrier reactions. Finally, we also explore modifications to nonadiabatic dynamics and conclude that, for this particular model, the presence of a large number of dark states yields negligible changes. Our study reveals new possibilities as well as limitations for the emerging field of polariton chemistry. |
Databáze: | OpenAIRE |
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