Milla Jovovich is expressing an "I just remembered" gesture along with fairly classic surprise here (Surprise is the most evanescent of all the emotions. It is extremely common for surprise to rapidly transition to fear, anger, sadness, embarrassment and others. Her eyes were probably opened wider a second before this photo was taken.). These hand positions (tips of fingers touching the temple area) are also a sign you will see when people are trying to remember or in mentally concentrating - although, unlike Milla's face, their facial expression will be more consistent with deep thought and be absent of the surprise component.
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