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Title: Controversial electronic structures and energies of Fe{sub 2}, Fe{sub 2}{sup +}, and Fe{sub 2}{sup −} resolved by RASPT2 calculations

The diatomic molecule Fe{sub 2} was investigated using restricted active space second-order perturbation theory (RASPT2). This molecule is very challenging to study computationally because predictions about the ground state and excited states depend sensitively on the choice of the quantum chemical method. For Fe{sub 2} we show that one needs to go beyond a full-valence active space in order to achieve even qualitative agreement with experiment for the dissociation energy, and we also obtain a smooth ground-state potential curve. In addition we report the first multireference study of Fe{sub 2}{sup +}, for which we predict an {sup 8}Σ{sub u}{sup −} ground state, which was not predicted by previous computational studies. By using an active space large enough to remove the most serious deficiencies of previous theoretical work and by explicitly investigating the interpretations of previous experimental results, this study elucidates previous difficulties and provides – for the first time – a qualitatively correct treatment of Fe{sub 2}, Fe{sub 2}{sup +}, and Fe{sub 2}{sup −}. Moreover, this study represents a record in terms of the number or active electrons and active orbitals in the active space, namely 16 electrons in 28 orbitals. Conventional CASPT2 calculations can be performed with at mostmore » 16 electrons in 16 orbitals. We were able to overcome this limit by using the RASPT2 formalism.« less
Authors:
; ; ;  [1]
  1. Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, 207 Pleasant St. SE, Minneapolis, Minnesota 55455-0431 (United States)
Publication Date:
OSTI Identifier:
22413243
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 20; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; DIAGRAMS; DISSOCIATION ENERGY; ELECTRONIC STRUCTURE; ELECTRONS; EXCITED STATES; GROUND STATES; MOLECULES; SPACE