Zappa's lead in to Po'Jama People is smokin' hot. That's the one I play for people who say, "Oh sure, he's technically perfect, but he has no soul." It really puts the lie to that.
Of the full length solos, I think Steve Vai, For the Love of God is incredible.
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Light a man a fire, and he will be warm while it burns.
Set a man on fire, and he will be warm for the rest of his life.
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