Can electrons change principal quantum number upon excitation?

I wanted to know when can excitation of electron take place i.e excitation of electron only takes place between subshells having same principal quantum number or is it seen by difference in energy level?  

For example look at configuration of Pt- [Xe] 6s2 4f14 5d8. It has vacant 5f, 6d, 6p. I know Pt is a noble metal and generally excitation may not take place, but for a moment let us forget it and assume excitation can take place. Can electrons of 6s excite to 5f? Or only 6d and 6p. Can electrons of 4f excite to 6d or 6p?


