This sounds very interesting but seems quite challenging. As you know, all electrochemical reactions take place at electrified intrefaces (liquid/solid, solid/solid). The Electric filed may modify the interaction between redox species and working electrode as well as the charge distribution at interfaces. You might be able to do it, if you could convert Electric field effect into other parameters such as the charge distribution or/and potential drop. I guess the Electric field effect could be significant in the solid-state electrochemistry.

If you use Gaussian 09 the keyword is Filed