Excited electronic states of MnO4−: Challenges for wavefunction and density functional response theories

Nuno M.S. Almeida, Russell G. Mckinlay, Martin J. Paterson

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Abstract

The lowest excited electronic states of the permanganate ion MnO4− are calculated using a hierarchy of coupled cluster response approaches, as well as time-dependent density functional theory. It is shown that while full linear response coupled cluster with singles and doubles (or higher) performs well, that permanganate represents a stern test for approximate coupled cluster response models, and that problems can be traced to very large orbital relaxation effects. TD-DFT is reasonably robust although errors around 0.6 eV are still observed. In order to further investigate the strong correlations prevalent in the electronic ground state large-scale RASSCF calculations were also performed. Again very large orbital relaxation in the correlated wavefunction is observed. Although the system can qualitatively be described by a single configuration, multi-reference diagnostic values show that care must be taken in this and similar metal complexes.
Original languageEnglish
Pages (from-to)86-91
Number of pages6
JournalChemical Physics
Volume446
Early online date20 Nov 2014
DOIs
Publication statusPublished - 13 Jan 2015

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