I think this might be a bit shabby on the performance end but I can see the benefit from the forum goers. Basically what you would have to do is on input from a new reply, thread or post edit, query all user names from the users table. Once done, check the names array against the "whole" words in the post. As the matches are made you would store an array of their relative user IDs. Finally, you'd progressively fire off the PMs in a while loop to those who (I would assume) was willing to receive such responses via PM. As an administrative tool, you'd probably have the ability to "walk backwards" and cycle through many posts performing the same task. If you'd like to go deeper, you might even create a scheduled task for doing so. Nice idea Elenna.
I might have to take you up on it.