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I've enabled the root account by setting a password for it but not matter what I try I cant log into any DE but the default unity one, while any other user (but root) can choose any DE

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Please edit your question to include what you're trying to accomplish (IE why you want to log in as root) - we'd be happy to help you find a way to do what you need to do without breaking everything or compromising the security of your computer. – David Oneill Apr 17 '12 at 19:36
For the record, I know how to do this. But I'm not posting an answer because I agree that this is a monumentally BAD idea. – Aaron Apr 17 '12 at 20:11

You can't log in to the GUI as root as it is an astronomically bad thing to do. Log on as a normal user and use sudo <command> if you really require root privileges. I've been using various kinds of Unix and Linux for 20 years and never had to log on to the GUI as root.

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This is impossible to do because if it did allow you do to do that MANY things wouldn't work correctly.

Any reason you might have for wanting to do this stems from misunderstanding something.

For a discussion about why not to log in as root, see Why is it bad to run as root?

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