Yes. The reason black-body radiation has such a distinct distribution is because you have a large number of particles trading energy with each other in thermal equilibrium.
>Does this blackbody radiation released from the inner atoms excite or heat the surface atoms slightly?
Well in an infinite system (or I suppose an insulated system surrounded by perfect mirrors at absolute zero or the same temperature as the interior), everyone is just passing energy to one another and the average energy of everyone follows something like a Maxwellian distribution and every spot is perfectly identical. When you have a surface the surface atoms are basically "dropping the ball" and throwing some of their light out of the system and off into the infinite unknown. As a result, they get colder. The inner atoms still pass their energy to the surface atoms, but now they're getting less of that energy back in return (since the surface atoms are colder) and thus the inner atoms start to cool. Thus we have heat loss through thermal radiation.