The emerging field of polaritonic chemistry explores the behavior of molecules under strong coupling with cavity modes. Despite recent developments in ab initio polaritonic methods for simulating polaritonic chemistry under electronic strong coupling, their capabilities are limited, especially in cases where the molecule also features strong electronic correlation. To bridge this gap, we have developed a novel method for cavity QED calculations utilizing the Density Matrix Renormalization Group (DMRG) algorithm in conjunction with the Pauli-Fierz Hamiltonian. Our approach is applied to investigate the effect of the cavity on the S0-S1 transition of n-oligoacenes, with n ranging from 2 to 5, encompassing 22 fully correlated π orbitals in the largest pentacene molecule. Our findings indicate that the influence of the cavity intensifies with larger acenes. Additionally, we demonstrate that, unlike the full determinantal representation, DMRG efficiently optimizes and eliminates excess photonic degrees of freedom, resulting in an asymptotically constant computational cost as the photonic basis increases.

Department of Chemistry University of North Carolina Charlotte Charlotte North Carolina 28223 United States

Department of Chemistry University of Washington Seattle Washington 98195 United States

Faculty of Mathematics and Physics Charles University 12116 Prague 2 Czech Republic

J Heyrovský Institute of Physical Chemistry Academy of Sciences of the Czech Republic v v i Dolejškova 3 18223 Prague 8 Czech Republic

Physical and Computational Sciences Directorate Pacific Northwest National Laboratory Richland Washington 99352 United States

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