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The song Black Sabbath off their first album. Much like Zep's first song, it really made an impact upon people then, that might be hard to understand for those who weren't teens back then. All I can say is, "Wow"!
Maybe Smells Like Teen Spirit from Nevermind is similar for the grunge age teens. Either way it is another great opening song for an album.
Maybe Golden Age of Rock and Roll from Mott the Hoople (The Hoople album)
"Gates of Delirium," "Ritual" & "Closer to the Edge" by Yes. These tracks are so freaking good that they don't need follow-up tracks!
+1 to Tom Sawyer and Power of Equality. I'll add:
Shake Me Like a Monkey from the latest DMB album
Stacked Actors from Foos' "There is Nothing Left to Lose"
Cherub Rock from Pumpkins' "Siamese Dream"
I've Been to Memphis from Lyle Lovett's "Joshua Judges Ruth"
I think there is a psychology behind opening tracks that we may be losing in this age of digital single downloads. Great opening tracks are not usually singles (despite a couple of my examples) but are usually high-energy tracks that grab attention quickly and define a band's sound. If the single is what the band wrote to break radio, the opening track is what they wrote to tell the world who they are and what the album is about.