Year: 2024
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide 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 S 0 –S 1 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.
Language: English
Subfield: Atomic and Molecular Physics, and Optics
Field: Physics and Astronomy
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
Funders: National Science Foundation, U.S. Department of Energy, Battelle, Univerzita Karlova v Praze, Grantová Agentura, Univerzita Karlova, European Commission, Ministerstvo Školství, Mládeže a Tělovýchovy, Grantová Agentura České Republiky, Office of Science, Division of Chemistry, Basic Energy Sciences, Pacific Northwest National Laboratory
Awards: G106018857, G1761812275, G2677629327, G2678520069, G2988778103, G3810236772, CAREER: Computational design of nanophotonic reagents, On-surface synthesis and characterization of polyradical molecules, G4396925471, G440375865, G484704822, G5290895463, G569086322, G5726405315, G5960638817, G5986892838, G6165425573, G6597962636, G6671297155, G721066557, G7851201386, G8227998441, G8718389019, G875823593, G8833608097, G941802975
OpenAlex ID: W4403703290