Divorced wife sneaking into husbands house is a physical control problem.
Spectorsoft makes good software to record what is being done ON the computer....chatting in IMs, what websites are being hit, watching porn, what e-mails are being sent/received/typed, etc. But you can't see WHO is doing it. This software is usually used when suspicion of cheating is going on, BEFORE the divorce..when you're still living with the person.
If you want to catch someone snooping on someone elses PC..you have to have a camera watching the PC itself. In this case, you're talking about a couple that divorcED already...as in past tense. And she is sneaking into his house. That is breaking and entering. His problems aren't his computer and e-mails...after all, they are divorced...he can do whatever he wants. His problem is having his home broken into. His solution is to get an alarm system with cameras..get a picture of his ex wife coming onto his property and breaking into his home, and get the police involved.
On the budget side...pickup an IP camera that starts recording when tripped...and will send him an e-mail with a picture as soon as it's tripped. He'll get it on his cell phone within a minute.