In Search of Organic Compounds Presenting a Double Exchange Phenomenon.

Abstract

The objective of this paper is to design a consistent series of organic molecules that may present a double exchange mechanism and study their low energy spectrum using spin unrestricted Density Functional Theory. For this purpose, organic tetra-methylene methane units having an S = 1 spin ground state and diamagnetic organic bridges are taken as building blocks for constructing molecules having two or more magnetic units. When biunit systems are ionized, the ground state of the resulting molecular ions may be either a quartet, if the spectrum is ruled by a double exchange mechanism, or a doublet, if it obeys the logic of a monoelectronic picture. A strategy based on the physical analysis of the leading interactions is followed in order to energetically favor a high-spin ground state. It is shown that the most promising compounds involve bridges that have both a large gap between the highest occupied and the lowest unoccupied molecular orbitals and small coefficients on the atoms to which the magnetic units are connected. While the followed strategy enables one to conceive organic compounds exhibiting a double exchange phenomenon, it is shown that the electronic mechanism ruling the spectrum of such organic double exchange compounds is different from that of their inorganic homologues. A new method to reconstruct the spectrum of low energy from various spin unrestricted DFT solutions is proposed and applied. Finally monodimensional and bidimensional periodic lattices based on the most promising organic architecture are suggested.