I would say "when I arrive home".
"At home" generally means "in your home" and is used to indicate a place where you are located rather than a destination.
Example: I was at home last night. When will you be at home? I left my wallet at home.
On the other hand, we often say "to arrive at" a destination. Ex: When did he arrive at the airport? So I think you could say either "arrive home" or "arrive at home".