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The powerful and expensive Staff of the Hierophant says in its description
The staff is also a +2/+2 quarterstaff and its wielder may use it to smite opponents. If one charge is expended (as a free action), the staff does double damage (x3 on a critical hit) for one round.
Does this mean the wielder can smite any enemy, every enemy (one at a time) all day long without using charges?
Does this language assume that your full character stats are used for this smite and aren't limited in some way? (So an oracle or sorcerer could get crazy benefits from the +Cha to deflection AC, for example)
No, the sentence about smiting is flavor text for the ability to spend a charge to deal double damage.
It is not the Smite Evil class feature or anything else like that.