On the possibility of STM-control of dissociative electron transfer

A novel physical mechanism of control of the rate of the electrochemical dissociative electron transfer with the use of the in situ STM arrangement is proposed. The mechanism consists of the electron tunneling between the substrate electrode and STM tip via the anti-bonding orbital of the molecule. A model for the theoretical description of this system is presented allowing calculation of the adiabatic Gibbs energy surface and the average occupation of the anti-bonding orbital of the molecule.