Density functional theory based calculations of the transfer integral in a redox-active single molecule junction

Abstract

There are various quantum chemical approaches for an ab initio description of transfer integrals within the framework of Marcus theory in the context of electron transfer reactions. In our article we aim to calculate transfer integrals in redox-active single molecule junctions, where we focus on the coherent tunneling limit with the metal leads taking the position of donor and acceptor and the molecule acting as a transport mediating bridge. This setup allows us to derive a conductance, which can be directly compared with recent results from a non-equilibrium Green's function approach. Compared with purely molecular systems we face additional challenges due to the metallic nature of the leads, which rules out some of the common techniques, and due to their periodicity, which requires {\bf k} space integration. We present three different methods, all based on density functional theory, for calculating the transfer integral under these constraints, which we benchmark on molecular test systems from the relevant literature. We also discuss manybody effects and apply all three techniques to a junction with a Ruthenium complex in different oxidation states.

References in corpus (5)

• Delta Self-Consistent Field as a method to obtain potential energy surfaces of excited molecules on surfaces
• Fermi level alignment in molecular nanojunctions and its relation to charge transfer
• Hot electron mediated desorption rates calculated from excited state potential energy surfaces
• Towards a theoretical description of molecular junctions in the Coulomb blockade regime based on density functional theory
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Cited by in corpus (5)

• Field-induced Conductance Switching by Charge-state Alternation in Organometallic Single-Molecule Junctions
• Destructive quantum interference in electron transport: A reconciliation of the molecular orbital and the atomic orbital perspective
• A density functional theory based direct comparison of coherent tunnelling and electron hopping in redox-active single molecule junctions
• Quantum interference in coherent tunnelling through branched molecular junctions containing ferrocene centers
• A Density Functional Theory Based Electron Transport Study of Coherent Tunneling Through Cyclic Molecules Containing Ru and Os as Redox Active Centers