Jump to main content
Jump to site search
Access to RSC content Close the message box

Continue to access RSC content when you are not at your institution. Follow our step-by-step guide.


Issue 19, 2017
Previous Article Next Article

A multiconfigurational approach to the electronic structure of trichromium extended metal atom chains

Author affiliations

Abstract

Density functional theory, Complete Active Space Self-Consistent Field (CASSCF) and perturbation theory (CASPT2) methodologies have been used to explore the electronic structure of a series of trichromium Extended Metal Atom Chains (EMACS) with different capping ligands. The study is motivated by the very different structural properties of these systems observed in X-ray experiments: the CN-capped example has a symmetric Cr3 unit while for the NO3-capped analogue the same unit has two very different Cr–Cr bond lengths. Density functional theory fails to locate an unsymmetric minimum for any of the systems studied, although the surface corresponding to the asymmetric stretch is very flat. CASPT2, in contrast, does locate an unsymmetric minimum only for the NO3-capped system, although again the surface is very flat. We use the Generalized active space (GASSCF) technique and effective Hamiltonian theory to interrogate the multi-configurational wavefunctions of these systems, and show that the increase in the σ–σ* separation as the chain becomes unsymmetric plays a defining role in the stability of the ground state and its expansion in terms of configuration state functions.

Graphical abstract: A multiconfigurational approach to the electronic structure of trichromium extended metal atom chains

Back to tab navigation

Supplementary files

Article information


Submitted
27 Mar 2017
Accepted
14 Apr 2017
First published
17 Apr 2017

This article is Open Access

Dalton Trans., 2017,46, 6202-6211
Article type
Paper

A multiconfigurational approach to the electronic structure of trichromium extended metal atom chains

M. Spivak, V. Arcisauskaite, X. López, J. E. McGrady and C. de Graaf, Dalton Trans., 2017, 46, 6202
DOI: 10.1039/C7DT01096F

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

Reproduced material should be attributed as follows:

  • For reproduction of material from NJC:
    [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
  • For reproduction of material from PCCP:
    [Original citation] - Published by the PCCP Owner Societies.
  • For reproduction of material from PPS:
    [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
  • For reproduction of material from all other RSC journals:
    [Original citation] - Published by The Royal Society of Chemistry.

Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.


Social activity

Search articles by author

Spotlight

Advertisements