Intramolecular charge ordering in the multi molecular orbital system (TTM-TTP)I3.
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.
Laboratoire de Chimie, Ecole Normale Supérieure de Lyon, Université de Lyon, CNRS, 46 Allée d'Italie, F-69364 Lyon, France.
Marie-Laure
ML
Bonnet
Vincent
V
Robert
Masahisa
M
Tsuchiizu
Yukiko
Y
Omori
Yoshikazu
Y
Suzumura
D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000737:chemistry*; D007455:Iodine / Q000737:chemistry*; D008280:Magnetics; D015394:Molecular Structure; D011789:Quantum Theory; D013440:Sulfides / Q000737:chemistry*; D013696:Temperature
D019086:Bridged Bicyclo Compounds, Heterocyclic; D013440:Sulfides; D007455:Iodine