A Fock-operator complete active space self-consistent field (CAS-SCF) method combined with frozen-density embedding

Schieschke, Nils; Bodenstein, Tilmann; Höfener, Sebastian

doi:10.1063/5.0037088

Cited by 4 publications

(2 citation statements)

References 51 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Both ground and local (uncoupled) excited states have been addressed in recent work by Höfener and co‐workers employing methods such as Full CI and truncated CI schemes embedded in a DFT environment (or with an additional layer described by MP2), 334 or complete‐active‐space self‐consistent field (CASSCF‐)in‐DFT embedding 335 …”

Section: Extensions Of Subsystem Density‐functional Theory and Frozen...mentioning

confidence: 99%

“…Both ground and local (uncoupled) excited states have been addressed in recent work by Höfener and co-workers employing methods such as Full CI and truncated CI schemes embedded in a DFT environment (or with an additional layer described by MP2), 334 or complete-active-space self-consistent field (CASSCF-)in-DFT embedding. 335 An alternative class of easy-to-use, black-box wavefunction methods for excited states can be defined in terms of the algebraic diagrammatic construction (ADC) scheme for the polarization propagator. 336 A first-time combination of FDET with ADC of second order (ADC [2]) in 2016 showed that complexation-induced shifts in dispersion-or hydrogen-bonded systems can be reproduced with good accuracy.…”

Section: Excited Statesmentioning

confidence: 99%

See 1 more Smart Citation

Subsystem density‐functional theory (update)

Jacob,

Neugebauer

2024

WIREs Comput Mol Sci

View full text Add to dashboard Cite

The past years since the publication of our review on subsystem density‐functional theory (sDFT) (WIREs Comput Mol Sci. 2014, 4:325–362) have witnessed a rapid development and diversification of quantum mechanical fragmentation and embedding approaches related to sDFT and frozen‐density embedding (FDE). In this follow‐up article, we provide an update addressing formal and algorithmic work on sDFT/FDE, novel approximations developed for treating the non‐additive kinetic energy in these DFT/DFT hybrid methods, new areas of application and extensions to properties previously not accessible, projection‐based techniques as an alternative to solely density‐based embedding, progress in wavefunction‐in‐DFT embedding, new fragmentation strategies in the context of DFT which are technically or conceptually similar to sDFT, and the blurring boundary between advanced DFT/MM and approximate DFT/DFT embedding methods.This article is categorized under: Electronic Structure Theory > Density Functional Theory

show abstract

Section: Extensions Of Subsystem Density‐functional Theory and Frozen...mentioning

confidence: 99%

Section: Excited Statesmentioning

confidence: 99%

Subsystem density‐functional theory (update)

Jacob,

Neugebauer

2024

WIREs Comput Mol Sci

View full text Add to dashboard Cite

show abstract

Quantum-derived embedding schemes for local excitations

et al. 2022

View full text Add to dashboard Cite

Quantum-mechanical (QM) and classical embedding models approximate a supermolecular quantumchemical calculation. This is particularly useful when the supermolecular calculation has a size that is out of reach for present QM models. Although QM and classical embedding methods share the same goal, they approach this goal from different starting points. In this study, we compare the polarizable embedding (PE) and frozen-density embedding (FDE) models. The former is a classical embedding model, whereas the latter is a density-based QM embedding model.Our comparison focuses on solvent effects on optical spectra of solutes. This is a typical scenario where super-system calculations including the solvent environment become prohibitively large. We formulate a common theoretical framework for PE and FDE models and systematically investigate how PE and FDE approximate solvent effects. Generally, differences are found to be small, except in cases where electron spill-out becomes problematic in the classical frameworks. In these cases, however, atomic pseudopotentials can reduce the electron-spill-out issue.

show abstract

Wavefunction frozen-density embedding with one-dimensional periodicity: Electronic polarization effects from local perturbations

Wachter-Lehn

Fink

Höfener

2022

The Journal of Chemical Physics

View full text Add to dashboard Cite

We report an approach to treat polarization effects in a one-dimensional (1D) environment using frozen-density embedding (FDE), suitable to compute response to electron loss or attachment as occurring in organic semi conductors during charge migration. The present work provides two key developments: (a) local perturbations are computed avoiding an infinite repetition thereof and (b) a first-order equation-of-motion (EOM) ansatz is used to compute polarization effects due to electron loss and attachment, ensuring an efficient calculation by avoiding open-shell calculations. In a first step, an unperturbed 1D molecular chain is equilibrated using FDE by translation of the center molecule. In a subsequent second step, long-range contributions are frozen and a local perturbation is introduced in the center subsystem. Freeze-Thaw iterations are used to relax the electronic wavefunction of both the center subsystem and subsystems in an active region around the center subsystem, avoiding the need to translate the perturbation. The proposed scheme renders to be very efficient and allows for the calculation charged tetraazaperopyrenes in 1D chains. Due to the efficiency, the new method can provide wavefunction-based reference data relevant for electronic couplings in complex environments.

show abstract

A Fock-operator complete active space self-consistent field (CAS-SCF) method combined with frozen-density embedding

Cited by 4 publications

References 51 publications

Subsystem density‐functional theory (update)

Subsystem density‐functional theory (update)

Quantum-derived embedding schemes for local excitations

Wavefunction frozen-density embedding with one-dimensional periodicity: Electronic polarization effects from local perturbations

Contact Info

Product

Resources

About