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I certainly wouldn't rank Hohenheim at the top though, he's definitely a genius despite his humble beginnings but the whole immortality was done by Father and Hohenheim really just picked up the scraps left from Father. We're given the impression that he is some super genius throughout the series but his backhistory kinda explains that away. His quick domination by Father after Father got serious shows who still is the master(although he did do better than anyone before him).
In regards to Mustang, we haven't really seen him put into a really intellectually spot. The only time I can think of was the switcharoo with Maria Ross. A good way of looking at it is that Mustang and Ed are on parallel paths. Ed is trying to deal with the intellectual side of Father while Mustang is dealing with the physical side(mainly running the country and taking control away from Bradley).
To be fair though, no regular alchemist would even be a State Alchemist due to the rigorous testing.
About Al, I would say he's the weakest alchemist of the 5 as it seems he got the physical talent over the alchemist skills in the family. Al is hard to compare as he is pretty much in the shadows against his brother who is a prodigy. However we have seen him pull some clever stuff out of his metal head such as his fight with Pride.
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