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The difference between XP and vista/w7 is prefetch and superfetch respectively.
In XP it will try to keep your ram as free as possible but will organize your HDD to launch your most use programs. In W7, superfetch is used, what it does is it keeps your most used programs in the ram available. So the more ram you have, the faster it'll be.
Off the top of my head, I haven't read the article in a long time that contains the info...so YMMV
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