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i dont see why it would matter....infact, if she's at work, it might make her day better if she DOES get asked out...just be careful how you do it..the wrong co-worker or her boss might see or hear and she could get in trouble.
It's better she doesn't work in your own dept. You don't have anything to lose, go for it. Just don't get your hopes too high or else you'll drown yourself.
the thing is.. if you aproach a girl while she's at work, the standard aproach probably isn't gonna work because if she's even the slightest bit attractive and works in a public place she's probably getting hit on quite a bit. you have to make yourself stand out from the crowd.