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That would be very useful; especially if you're battling a legendary. Rather than keeping its HP in the red zone and hoping your 20th Ultra Ball would succeed, you could defeat it outright and make as many capture attempts as the number of Poké Balls in your possession. Of course, the capture would still not be certain, but the probability should be a little better—the FNT condition would have a status modifier of 3 or 3.5 as opposed to SLP and FRZ which is 2 or 2.5. Some people would recommend limiting this mechanic to certain species (i.e. legendaries) as it might break the game.