This is really a fantastic suggestion! Pair programming can't be advocated enough. I used to think it was stupid many years ago, and then I made friends with a guy who'd been programming longer than I'd been alive. We'd both stay late and shared an office, and in the evenings he started mentoring me, and we'd pair program. I think there is no better way for bringing programmers up to speed (whether junior-senior or slow-fast or new-old or whatever). Also, having tried a variety of interviewing techniques, I find pair programming to have one of the highest concentrations of useful information about a candidate. Work sample being another.
Well, this was years ago, and we were working on different tasks during the workday. It started with me asking questions and him showing me how to do something that ended up being pair programming. Like many workplaces, there wasn't much time for teaching moments during the workday.