The Polarizable Embedding Density Matrix Renormalization Group Method

Abstract

The polarizable embedding (PE) approach is a flexible embedding model where a pre-selected region out of a larger system is described quantum mechanically while the interaction with the surrounding environment is modeled through an effective operator. This effective operator represents the environment by atom-centered multipoles and polarizabilities derived from quantum mechanical calculations on (fragments of) the environment. Thereby, the polarization of the environment is explicitly accounted for. Here, we present the coupling of the PE approach with the density matrix renormalization group (DMRG). This PE-DMRG method is particularly suitable for embedded subsystems that feature a dense manifold of frontier orbitals which requires large active spaces. Recovering such static electron-correlation effects in multiconfigurational electronic structure problems, while accounting for both electrostatics and polarization of a surrounding environment, allows us to describe strongly correlated electronic structures in complex molecular environments. We investigate various embedding potentials for the well-studied first excited state of water with active spaces that correspond to a full configuration-interaction treatment. Moreover, we study the environment effect on the first excited state of a retinylidene Schiff base within a channelrhodopsin protein. For this system, we also investigate the effect of dynamical correlation included through short-range density functional theory.

33 pages, 5 figures, 4 tables

References in corpus (16)

• The density-matrix renormalization group in the age of matrix product states
• From density-matrix renormalization group to matrix product states
• Automated Selection of Active Orbital Spaces
• Low-energy spectrum of iron-sulfur clusters directly from many-particle quantum mechanics
• The density matrix renormalization group for ab initio quantum chemistry
• A practical guide to density matrix embedding theory in quantum chemistry
• Applying matrix product operators to model systems with long-range interactions
• Entanglement Measures for Single- and Multi-Reference Correlation Effects
• The Delicate Balance of Static and Dynamic Electron Correlation
• A flexible multi-reference perturbation theory by minimizing the Hylleraas functional with matrix product states
• Spin-adapted Matrix Product States and Operators
• Matrix Product State applications for the ALPS project
• DMRG-CASPT2 study of the longitudinal static second hyperpolarizability of all-trans polyenes
• On the exact formulation of multi-configuration density-functional theory: electron density versus orbitals occupation
• Self-Consistent Embedding of Density-Matrix Renormalization Group Wavefunctions in a Density Functional Environment
• Local density approximation in site-occupation embedding theory

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