Intramolecular charge ordering in the multi molecular orbital system ( TTM-TTP ) I 3

Starting from the structure of the ( TTM-TTP ) I 3 molecular-based material, we examine the characteristics of frontier molecular orbitals using ab initio (CASSCF/CASPT2) configurations interaction calculations. It is shown that the singly occupied and second-highest-occupied molecular orbitals are...

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Published in:The Journal of chemical physics 2010-06, Vol.132 (21), p.214705-214705-6
Main Authors: Bonnet, Marie-Laure, Robert, Vincent, Tsuchiizu, Masahisa, Omori, Yukiko, Suzumura, Yoshikazu
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Summary:Starting from the structure of the ( TTM-TTP ) I 3 molecular-based material, we examine the characteristics of frontier molecular orbitals using ab initio (CASSCF/CASPT2) configurations interaction calculations. It is shown that the singly occupied and second-highest-occupied molecular orbitals are close to each other, i.e., this compound should be regarded as a two-orbital system. By dividing virtually the [TTM-TTP] molecule into three fragments, an effective model is constructed to rationalize the origin of this picture. In order to investigate the low-temperature, symmetry breaking experimentally observed in the crystal, the electronic distribution in a pair of [TTM-TTP] molecules is analyzed from CASPT2 calculations. Our inspection supports and explains the speculated intramolecular charge ordering which is likely to give rise to low-energy magnetic properties.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.3432764