I've tried before and haven't been able to do it successfully. Its because of the table that is used to hold the links, the popup menu is set to appear in the left hand side and I'm not sure if it is possible to calculate a centre position for which to align it to. (The problem can also be seen here on vBulletin.org - if you have a large resolution)
If you fit more links on the navbar then it made reduce the misalignment.
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