English
 
Help Privacy Policy Disclaimer
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT
  Magnetic exchange coupling in Cu dimers studied with modern multireference methods and broken-symmetry coupled cluster theory

Singh, G., Gamboa, S., Orio, M., Pantazis, D. A., & Roemelt, M. (2021). Magnetic exchange coupling in Cu dimers studied with modern multireference methods and broken-symmetry coupled cluster theory. Theoretical Chemistry Accounts, 140(10): 139. doi:10.1007/s00214-021-02830-0.

Item is

Basic

show hide
Genre: Journal Article

Files

show Files

Locators

show

Creators

show
hide
 Creators:
Singh, Gurjot1, Author
Gamboa, Stefani2, Author
Orio, Maylis2, Author
Pantazis, Dimitrios A.3, Author              
Roemelt, Michael1, Author              
Affiliations:
1Lehrstuhl Für Theoretische Chemie, Ruhr-Universität Bochum, 44780, Bochum, Germany, ou_persistent22              
2Institut des Sciences Moléculaires de Marseille, Aix Marseille Université, CNRS, Centrale Marseille, ISM2 UMR 7313, 13397, Marseille, France, ou_persistent22              
3Research Group Pantazis, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541711              

Content

show
hide
Free keywords: Exchange coupling; Copper; Multireference methods; Broken symmetry; Coupled cluster
 Abstract: Spin-state energetics of exchange-coupled copper complexes pose a persistent challenge for applied quantum chemistry. Here, we provide a comprehensive comparison of all available theoretical approaches to the problem of exchange coupling in two antiferromagnetically coupled bis-μ-hydroxo Cu(II) dimers. The evaluated methods include multireference methods based on the density matrix renormalization group (DMRG), multireference methods that incorporate dynamic electron correlation either perturbatively, such as the N-electron valence state perturbation theory, or variationally, such as the difference-dedicated configuration interaction. In addition, we contrast the multireference results with those obtained using broken-symmetry approaches that utilize either density functional theory or, as demonstrated here for the first time in such systems, a local implementation of coupled cluster theory. The results show that the spin-state energetics of these copper dimers are dominated by dynamic electron correlation and represent an impossible challenge for multireference methods that rely on brute-force expansion of the active space to recover correlation energy. Therefore, DMRG-based methods even at the limit of their applicability cannot describe quantitatively the antiferromagnetic exchange coupling in these dimers, in contrast to dinuclear complexes of earlier transition metal ions. The convergence of the broken-symmetry coupled cluster approach is studied and shown to be a limiting factor for the practical application of the method. The advantages and disadvantages of all approaches are discussed, and recommendations are made for future developments.

Details

show
hide
Language(s): eng - English
 Dates: 2021-07-022021-09-202021-10-01
 Publication Status: Published in print
 Pages: 15
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1007/s00214-021-02830-0
 Degree: -

Event

show

Legal Case

show

Project information

show

Source 1

show
hide
Title: Theoretical Chemistry Accounts
  Abbreviation : Theor. Chem. Acc.
Source Genre: Journal
 Creator(s):
Affiliations:
Publ. Info: Heidelberg : Springer-Verlag
Pages: - Volume / Issue: 140 (10) Sequence Number: 139 Start / End Page: - Identifier: ISSN: 1432-881X
CoNE: https://pure.mpg.de/cone/journals/resource/954925623262