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Oh lovely, in noooo way could this go wrong...Note: Rimuru has now been changed to Light Novel version.
It depends. In this case the "soul possession" is absorption that seems extremely vague. It could potentially require the soul to actually be damaged during the consumption process, like how humans eat/devour food, in which case it wouldn't really work.
The thing is, will he be doing this to both Rimuru and Reinhard? Reinhard ain't the only one in the matchup. Can he fend off them both at once?
Cause like...
1. Match starts
2. Ainz, Rimuru, and Reinhard see each other a medium distance away.
3. Reinhard's first move is to swing his sword. Rimuru's first move is to analyze and then use whatever ability would work best for him.
In order for Ainz to win, he must do something that immediately eliminates Reinhard as a threat. Is his first move 100% of the time going to be something that does that? If not, what would the percent look like?
Can you prove it does? No, not in this case, cause we don't know and assuming is a bad thing to do.
Rimuru dies in Ainz' opening move lmfao, he's still got baseline Death resistance from what I'm seeing
If you actually read Ainz Ooal Gown's profile, you'd see his opening move most often is Time Stop. From there he can make Christmas trees of spells of the opponents to test their Resistances. This includes Death Manipulation. Rimuru dies in the opening act and if Ainz chooses to stand next to Reinhard he dies from Despair Aura V repeatedly and is incapped. And if he remains any decent amount of time Dead the first time, Reinhard is getting looted. Ainz probably steals Reid off of Reinhard's corpse first thing lol
Ainz loves his magical artifacts you know!