Irina Petreska, Ljupčo Pejov, Ljupčo Kocarev


In this paper results from ab initio simulations of the electronic structure properties of a class of halogenated phenylene ethynylene oligomers (OPE) are presented. These molecular species are investigated because of their suitable properties for application as single-molecule switches in the future emerging molecular electronic devices. Combined Hartree-Fock and Density Functional Theory approach is applied to investigate the biasing field effects on the relevant electronic properties, such as potential energy of the ground states, potential barrier height, localization of frontier molecular orbitals and the HOMO-LUMO gap. Special attention is also paid on the effects of substitution of the hydrogen atoms in the central phenylene ring of basic OPE molecule with halogen atoms. The analyses of the obtained results undoubtedly show that the biasing field has a strong impact on the potential barrier height, transition probabilities and band gap. Halogenation of the central phenylene ring does not have such a strong influence on the aforementioned properties, but it could be a useful way for fine tuning of some of the properties, especially the potential barrier height, enabling control of the torsional stochastic switching, inherent for the studied species.


ab initio; phenylene ethynylene; single-molecule switches; Hartree-Fock; Density Functional Theory; potential barrier; frontier molecular orbitals; HOMO-LUMO gap; torsional stochastic switching

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