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Discord does not natively allow you to link your PS account; any sort of link would require 3rd party infrastructure, which to my knowledge is not currently provided in any official capacity by Smogon (I hope to change that).
If you're trying to verify your Discord account so you can...
I don't know the exact mechanics, but from what I recall from when I did it years ago, the advancements are odd here. It seems to consistently gravitate toward certain frames, which basically means that some frames aren't hittable, and doing more Chatot calls might end up landing you on an...