TY  - JOUR
AU  - Sidler, Dominik
AU  - Schäfer, Christian
AU  - Ruggenthaler, Michael
AU  - Rubio, Angel
TI  - Polaritonic Chemistry: Collective Strong Coupling Implies Strong Local Modification of Chemical Properties
JO  - The journal of physical chemistry letters
VL  - 12
IS  - 1
SN  - 1948-7185
CY  - Washington, DC
PB  - ACS
M1  - PUBDB-2021-00408
SP  - 508 - 516
PY  - 2021
AB  - A fundamental question in the field of polaritonic chemistry is whether collective coupling implies local modifications of chemical properties scaling with the ensemble size. Here we demonstrate from first-principles that an impurity present in a collectively coupled chemical ensemble features such locally scaling modifications. In particular, we find the formation of a novel dark state for a nitrogen dimer chain of variable size, whose local chemical properties are altered considerably at the impurity due to its embedding in the collectively coupled environment. Our simulations unify theoretical predictions from quantum optical models (e.g., collective dark states and bright polaritonic branches) with the single molecule quantum chemical perspective, which relies on the (quantized) redistribution of charges leading to a local hybridization of light and matter. Moreover, our findings suggest that recently developed ab initio methods for strong light-matter coupling are suitable to access these local polaritonic effects and provide a detailed understanding of photon-modified chemistry.
LB  - PUB:(DE-HGF)16
C6  - 33373238
UR  - <Go to ISI:>//WOS:000667301800023
DO  - DOI:10.1021/acs.jpclett.0c03436
UR  - https://bib-pubdb1.desy.de/record/454077
ER  -