PokéBase - Pokémon Q&A
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If he appears randomly, then what is the chance of him appearing? Please don't question my curiosity.

closed with the note: Very trivial and finding an answer would take too much work for what it's worth.
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"Professor Rowan can occasionally be found here hoping to buy Rage Candy Bars" thanks bulbapedia
!'•-Indigo-•'! is it fine if I put the link to prove that u are right I don't deserve best answer though you do.
That doesn't answer the question, though. Indigo only posted about it to mock how unhelpful it is.
When exactly does he appear wanting to buy items? All Bulbapedia does is explain why he appears at all.