2024-12-10 パシフィック・ノースウェスト国立研究所(PNNL)
＜関連情報＞
- https://www.pnnl.gov/publications/polaritonic-chemistry-density-matrix-renormalization-group-method
- https://pubs.acs.org/doi/10.1021/acs.jctc.4c00986
密度行列繰り込み群法を用いたポラリトン化学 Polaritonic Chemistry Using the Density Matrix Renormalization Group Method
Mikuláš Matoušek,Nam Vu,Niranjan Govind,Jonathan J. Foley IV,and Libor Veis,,
Journal of Chemical Theory and Computation Published: October 23, 2024
DOI:https://doi.org/10.1021/acs.jctc.4c00986
Abstract
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.
