This would be a neat way to catch a laptop thief.
Probably not with PhotoBooth though :)
I know a smart lady who (after reading about webcams on compromised machines being used to take snaps without the knowledge of unsuspecting users) used a simple fix; stick a bindi(http://commons.wikimedia.org/wiki/File:Bindi.jpg) on the webcam.
iTried listens for screensaver stopped events, and then takes the picture. I disabled tweetpic'ing the picture when submitting to the app store, but will re-enable in an update.