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Apollo
Article . 2024
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Apollo
Article . 2024
License: CC BY
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The Journal of Chemical Physics
Article . 2024 . Peer-reviewed
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https://dx.doi.org/10.48550/ar...
Article . 2024
License: arXiv Non-Exclusive Distribution
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CanGWhandle multireference systems?

Authors: Ammar, Abdallah; Marie, Antoine; Rodríguez-Mayorga, Mauricio; Burton, Hugh GA; Loos, Pierre-François;

CanGWhandle multireference systems?

Abstract

Due to the infinite summation of bubble diagrams, the GW approximation of Green’s function perturbation theory has proven particularly effective in the weak correlation regime, where this family of Feynman diagrams is important. However, the performance of GW in multireference molecular systems, characterized by strong electron correlation, remains relatively unexplored. In the present study, we investigate the ability of GW to handle closed-shell multireference systems in their singlet ground state by examining four paradigmatic scenarios. First, we analyze a prototypical example of a chemical reaction involving strong correlation: the potential energy curve of BeH2 during the insertion of a beryllium atom into a hydrogen molecule. Second, we compute the electron detachment and attachment energies of a set of molecules that exhibit a variable degree of multireference character at their respective equilibrium geometries: LiF, BeO, BN, C2, B2, and O3. Third, we consider a H6 cluster with a triangular arrangement, which features a notable degree of spin frustration. Finally, the dissociation curve of the HF molecule is studied as an example of single bond breaking. These investigations highlight a nuanced perspective on the performance of GW for strong correlation depending on the level of self-consistency, the choice of initial guess, and the presence of spin-symmetry breaking at the Hartree–Fock level.

Countries
United Kingdom, France
Keywords

Chemical Physics (physics.chem-ph), Condensed Matter - Materials Science, Nuclear Theory, Strongly Correlated Electrons (cond-mat.str-el), 34 Chemical Sciences, Materials Science (cond-mat.mtrl-sci), FOS: Physical sciences, 530, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Nuclear Theory (nucl-th), [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, Condensed Matter - Strongly Correlated Electrons, 5102 Atomic, Molecular and Optical Physics, Physics - Chemical Physics, 3406 Physical Chemistry, [PHYS.COND]Physics [physics]/Condensed Matter [cond-mat], 51 Physical Sciences, [PHYS.COND] Physics [physics]/Condensed Matter [cond-mat]

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selected citations
These citations are derived from selected sources.
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
17
Top 10%
Average
Top 10%
Green