Oh yeah...forgot to mention that when using older ANSI PST files, they can grow larger than 2GB and still work in Outlook. I've seen some as large as 3GB, believe it or not! But as soon as the user tries to remove, read, or edit old emails or documents stored in the PST, it is likely to become corrupted. At that point, you would have to follow the instructions laid out in nlm9802's link above.
I just wanted to make the point that a PST doesn't become corrupted immediately after it hits 2GB. In fact, some can become corrupted at 1.82GB, which is explained in the fourth link I posted above.