Vibrational detection and control of spin in mixed-valence molecular transistors

We investigate electron transport through a mixed-valence molecular complex in which an excess electron can tunnel between heterovalent transition metal ions, each having a fixed localized spin. We show that in this class of molecules the interplay of the spins and the vibrational breathing modes of the ionic ligand shells allows the total molecular spin to be detected as well as controlled by nonequilibrium transport. Due to a spin-dependent pseudo-Jahn-Teller effect electronic transitions with different spin values can be distinguished by their vibronic conductance side peaks, without using an external magnetic field. Conversely, we show that the spin state of the entire molecule can also be controlled via the nonequilibrium quantized molecular vibrations due to a vibration-induced spin blockade.