I don't know if you can hook directly into the PDC's security layer the way you are saying and even if you could, I don't know that you'd want to (the security APIs will give any programmer a headache to end all headaches . . . I'm still recovering from my encounter).
What I would do if I were you would be to have the user's Login Script run an executable. This executable would run on the user's machine and it would use some basic APIs to get local user name, machine name, time, and date (etc etc). This data would then be recorded to a database somewhere (perhaps a small DB located on the PDC or anywhere else on you network). This would give a complete log of who is logging in, where they are logging in from, and what time they are logging in at. If you want to know what APIs you will need to get the machine name and user name, just let me know and I will look them up for you. They are pretty easy to use however.