Yes they can, but you have to understand it's not likely. The people who represent each state on the electoral college are chose by the state party organization of the winning candidate. So, in order for that to happen, someone who was chosen BY the state republican or state democratic party would have to then go and vote otherwise, which would also, in most cases, guarantee they would never be chosen for anything by that party again. It's VERY unlikely.
EDIT: And if any of that is going to happen this election, it will be the other way around. People chosen as the Republican party electors who don't feel comfortable voting for Bush and voting for Kerry, or someone completely different instead so as not to give their vote to ANYONE.
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