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FB - I agree. I travel by train a lot in Europe and think it's a great way to travel. If the OP is interested in this, check out Rail Europe for tickets/passes and http://www.seat61.com for a good travel website that is aimed at people travelling by train.
Quite so Cougie,apart from the hitmen, it's a great city!
I like Bruges but I'm not sure I'd want to do 3-5 days there - you can see most the city has to offer in a day or 2. combining it with a trip to Ghent would work as that's not far away (about 50km and you could train between) - it's as good as Bruges but without being so "picture postcard" (fewer canals, slightly more industrial).
lots of good suggestions, Barcelona, Rome and Berlin I can recommend.Love Italian cities - Florence was superb (and you can combine it with Pisa), and did a 3 dayer in Milan. Both beautiful and easy to wander around.
Nobody has said Munich so i'll drop that in along with Salzburg. Both very interesting places and a lot to offer. Both only 2 or 3 hours away
Thanks everyone, they've decided to go to Berlin.