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I would assume it would only add to one barrel. The way I've read it by using it as many shot, only one gets the bonus when you crit but now that I think of it, isn't smite for every attack till the opponent is defeated? So in that case each shot would. I use it on my pistoleer and with rapid shot and firing each barrel, for a -6 with each shot I can do 4d8+28 at 6th