I dont know about a program but certain motherboards have an option to do this in the bios like the abit sh6.
I dont think there is away to have a program execute it self at bios level.So you might be able do it only if your bios supports it.
some asus m/bs also have it its a nice feature.. personally i'd rather the mouse be the on button.. ah well i leave my comp on all the time so its a useless feature
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