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  Spin-state energetics of manganese spin crossover complexes: Comparison of single-reference and multi-reference ab initio approaches

Drosou, M., Mitsopoulou, C. A., & Pantazis, D. A. (2021). Spin-state energetics of manganese spin crossover complexes: Comparison of single-reference and multi-reference ab initio approaches. Polyhedron, 208(11): 115399. doi:10.1016/j.poly.2021.115399.

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 Creators:
Drosou, Maria1, Author
Mitsopoulou, Christina A.1, Author
Pantazis, Dimitrios A.2, Author              
Affiliations:
1Inorganic Chemistry Laboratory, National and Kapodistrian University of Athens, Panepistimiopolis, Zografou 15771, Greece, ou_persistent22              
2Research Group Pantazis, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541711              

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Free keywords: Spin-state energetics; Spin crossover; Coupled cluster theory; Multireference calculations; DFT
 Abstract: Manganese spin crossover (SCO) complexes form a small but ever expanding family of compounds with thermally accessible states of different electronic configuration and total spin. Accurate prediction of spin-state energetics is essential for the theoretical description of these systems. However, this represents a challenging problem that necessitates recourse to correlated wave function methods rather than the more approximate density functional theory (DFT). Here we present a detailed study of spin-state energetics for eight Mn(III) and Mn(II) SCO complexes using the domain-based local pair natural orbital approach to coupled cluster theory with singles, doubles, and perturbative triples, DLPNO-CCSD(T). The effects of reference determinants, basis set, triples excitations, and pair natural orbitals (PNO) thresholds are evaluated and analysed in detail, enabling us to propose a robust and efficient computational protocol based on a combined and balanced mix of extrapolation to the complete basis set and infinite PNO space limits. The results are subsequently used to evaluate multireference wavefunction-based (CASSCF/NEVPT2) and DFT approaches, highlighting their inability to provide a balanced description of spin-state energetics for these complexes. The DLPNO-CCSD(T) protocol proposed in this study can serve as a generally applicable reference-quality quantum chemical method for studying spin crossover systems.

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Language(s): eng - English
 Dates: 2021-04-252021-07-302021-11-01
 Publication Status: Published in print
 Pages: -
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1016/j.poly.2021.115399
 Degree: -

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Title: Polyhedron
  Abbreviation : Polyhedron
Source Genre: Journal
 Creator(s):
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Publ. Info: Oxford : Pergamon
Pages: - Volume / Issue: 208 (11) Sequence Number: 115399 Start / End Page: - Identifier: ISSN: 0277-5387
CoNE: https://pure.mpg.de/cone/journals/resource/954925622228_2