It's a candid picture taken at the end of a photo-op of the head of Nerv and the pilot of unit 01. Rei is waiting by her machine and Misako is just out of the shot.
Here's a bonus pic - a photo of Shinju-hime ( based on a gashapon figurine of Scarlett O'Hara St. Jones from Steam Boy)
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jsy something about the way she looks in the first pic that is just creepy looking. not sure what is wrong with it, but soimething about her face is really off that makes it just look really creepy. the other shot looks a bit better, but still off for some reason. but it is cool idea though.
Well there is something a teensy bit off about the eyes in the first picture. They are flat and level while her head is canted to the side. Its a bit off setting.