Functional Properties of Tetrameric Molecular Cells for Quantum Cellular Automata: A Quantum-Mechanical Treatment Extended to the Range of Arbitrary Coulomb Repulsion

We discuss the problem of electron transfer (ET) in mixed valence (MV) molecules that is at the core of molecular Quantum Cellular Automata (QCA) functioning. Theoretical modelling of tetrameric bi-electronic MV molecular square (prototype of basic QCA cell) is reported. The model involves interelectronic Coulomb repulsion, vibronic coupling and ET between the neighboring redox sites. Unlike the majority of previous studies in which molecular QCA have been analyzed only for particular case when the Coulomb repulsion energy significantly exceeds the ET energy, here we do not imply assumptions on the relative strength of these two interactions. Moreover, in the present work we go beyond the adiabatic semiclassical approximation often used in theoretical analysis of such systems in spite of the fact that this approximation ignores such an important phenomenon as quantum tunneling. By analyzing the electronic density distributions in the cells and the ell-cell response functions obtained from a quantum-mechanical solution of a complex multimode vibronic problem we have concluded that such key features of QCA cell as bistability and switchability can be achieved even under failure of the condition of strong Coulomb repulsion provided that the vibronic coupling is strong enough. We also show that the semiclassical description of the cell-cell response functions loses its accuracy in the region of strong non-linearity, while the quantum-mechanical approach provides correct results for this critically important region.

Automated summary

This study discusses the problem of electron transfer in mixed valence molecules, which is crucial for the functioning of molecular Quantum Cellular Automata (QCA). A theoretical model of tetrameric bi-electronic mixed valence molecular square is presented, taking into account interelectronic Coulomb repulsion, vibronic coupling, and electron transfer between neighboring redox sites. The results show that key features of QCA cells, such as bistability and switchability, can be achieved even when the Coulomb repulsion is not significantly stronger than the electron transfer energy, as long as the vibronic coupling is sufficiently strong.