Polaritonic Chemistry: Collective Strong Coupling Implies Strong Local Modification of Chemical Properties

ACS Nano (submitted), (2020)

Polaritonic Chemistry: Collective Strong Coupling Implies Strong Local Modification of Chemical Properties

Dominik Sidler, Christian Schäfer, Michael Ruggenthaler, Angel Rubio

Polaritonic chemistry has become a rapidly developing field within the last few years. A multitude of experimental observations suggest that chemical properties can be fundamentally altered and novel physical states appear when matter is strongly coupled to resonant cavity modes, i.e. when hybrid light-matter states emerge. Up until now, theoretical approaches to explain and predict these observations were either limited to phenomenological quantum optical models, suited to describe collective polaritonic effects, or alternatively to ab initio approaches for small system sizes. The later methods were particularly controversial since collective effects could not be explicitly included due to the intrinsically low particle numbers, which are computationally accessible. Here, we demonstrate for a nitrogen dimer chain of variable size that any impurity present in a collectively coupled chemical ensemble (e.g. temperature fluctuations or reaction process) induces local modifications in the polaritonic system. From this we deduce that a novel dark state is formed, whose local chemical properties are modified considerably at the impurity due to the collectively coupled environment. Our simulations unify theoretical predictions from quantum optical models (e.g. formation of collective dark states and different polaritonic branches) with the single molecule quantum chemical perspective, which relies on the (quantized) redistribution of local charges. Moreover, our findings suggest that the recently developed QEDFT method is suitable to access these locally scaling polaritonic effects and it is a useful tool to better understand recent experimental results and to even design novel experimental approaches. All of which paves the way for many novel discoveries and applications in polaritonic chemistry.

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The authors thank Johannes Flick, Enrico Ronca and Claudiu Genes for helpful discussions and critical comments. This work was made possible through the support of the RouTe Project (13N14839), financed by the Federal Ministry of Education and Research (Bundesministerium f¨ur Bildung und Forschung (BMBF)) and supported by the European Research Council (ERC-2015-AdG694097), the Cluster of Excellence ”CUI: Advanced Imaging of Matter” of the Deutsche Forschungsgemeinschaft (DFG), EXC 2056, project ID 390715994 and the Grupos Consolidados (IT1249-19). The Flatiron Institute is a division of the Simons Foundation.

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