New Density Matrix Renormalization Group Approaches for Strongly Correlated Systems Coupled with Large Environments

Yihe Xu; Yifan Cheng; Yinxuan Song; Haibo Ma

doi:10.1021/acs.jctc.2c01316

New Density Matrix Renormalization Group Approaches for Strongly Correlated Systems Coupled with Large Environments

J Chem Theory Comput. 2023 Aug 8;19(15):4781-4795. doi: 10.1021/acs.jctc.2c01316. Epub 2023 Jul 20.

Authors

Yihe Xu¹, Yifan Cheng¹, Yinxuan Song¹, Haibo Ma²

Affiliations

¹ School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China.
² Qingdao Institute for Theoretical and Computational Sciences, Qingdao Institute of Frontier and Interdisciplinary Science, Shandong University, Qingdao 266237, China.

PMID: 37471519
DOI: 10.1021/acs.jctc.2c01316

Abstract

Thanks to the high compression of the matrix product state (MPS) form of the wave function and the efficient site-by-site iterative sweeping optimization algorithm, the density matrix normalization group (DMRG) and its time-dependent variant (TD-DMRG) have been established as powerful computational tools in accurately simulating the electronic structure and quantum dynamics of strongly correlated molecules with a large number (10^1-2) of quantum degrees of freedom (active orbitals or vibrational modes). However, the quantitative characterization of the quantum many-body behaviors of realistic strongly correlated systems requires a further consideration of the interaction between the embedded active subsystem and the remaining correlated environment, e.g., a larger number (10^2-3) of external orbitals in electronic structure or infinite condensed-phase phononic modes in nucleus dynamics. To this end, we introduced three new post-DMRG and TD-DMRG approaches, namely (1) DMRG2sCI-MRCI and DMRG2sCI-ENPT by the reconstruction of selected configuration interaction (sCI) type of compact reference function from DMRG coefficients and the use of externally contracted MRCI (multireference configuration interaction) and Epstein-Nesbet perturbation theory (ENPT), without recourse to the expensive high order n-electron reduced density matrices (n-RDMs). (2) DMRG combined with RR-MRCI (renormalized residue-based MRCI), which improves the computational accuracy and efficiency of internally contracted (ic) MRCI by renormalizing the contracted bases with small-sized buffer environment(s) of a few external orbitals as probes based on quantum information theory. (3) HM (hierarchical mapping)-TD-DMRG in which a large environment is reduced to a small number of renormalized environmental modes (which accounts for the most vital system-environment interactions) through stepwise mapping transformation. These advances extend the efficacy of highly accurate DMRG/TD-DMRG computations to the quantitative characterization of the electronic structure and quantum dynamics in realistic strongly correlated systems coupled with large environments and are reviewed in this paper.

Publication types

Review