A Hückel source-sink-potential theory of Pauli spin blockade in molecular electronic devices

This paper shows how to include Pauli (exclusion principle) effects within a treatment of ballistic molecular conduction that uses the tight-binding Hückel Hamiltonian and the source-sink-potential (SSP) method. We take into account the many-electron ground-state of the molecule and show that we can discuss ballistic conduction for a specific molecular device in terms of four structural polynomials. In the standard one-electron picture, these are characteristic polynomials of vertex-deleted graphs, with spectral representations in terms of molecular-orbital eigenvectors and eigenvalues. In a more realistic many-electron picture, the spectral representation of each polynomial is retained but projected into the manifold of unoccupied spin-orbitals. Crucially, this projection preserves interlacing properties. With this simple reformulation, selection rules for device transmission, expressions for overall transmission, and partition of transmission into bond currents can all be mapped onto the formalism previously developed. Inclusion of Pauli spin blockade, in the absence of external perturbations, has a generic effect (suppression of transmission at energies below the Fermi level) and specific effects at anti-bonding energies, which can be understood using our previous classification of inert and active shells. The theory predicts the intriguing phenomenon of Pauli perfect reflection whereby, once a critical electron count is reached, some electronic states of devices can give total reflection of electrons at all energies.