Perhaps an example of what you mean can be seen with the noble gases. As you go from helium to neon to argon, etc. you are adding inner electron shells and making the electron cloud around each atom more polarizable. That in turn increases the van der Waals attraction between atoms, resulting in a dramatic increase in boiling points down the series.

You might be able to make an atom more polarizable (and increase van der Waals forces) by electronically exciting it to a higher energy level. Can anyone else elaborate on that possibility?

[![Boiling points of the noble gases increasing with atomic weight][]]