A better question that I always ask, before any other questions in the interview: "Why do you want to work here?" Then I reject any answer that's not somewhat unique to our business. "You could do that anywhere, is there anything specific to this place?" Then I probe the final answer to make sure it's not BS.
Bad answers: I've heard you make a lot of money here, I want to work on software development, I like Java. Better: I have friends who've told me about it and it sounds like the kind of place I want to work. The best answer: I understand a lot about how your business works and it is a win-win for me to be here for the following reasons... despite the following minuses...
I was playing Resistance this weekend for the first time. Essentially Resistance is Mafia with rules, blue vs. red. One of the first things I did was ask people, "are you a spy?" Like a melodramatic detective. I think there is an instinct to try this first, and win the game on the basis of a twitching lip or "say no, nod yes" sort of reaction.
This may work on easily startled people. Same with slamming your hand on the table in a security clearance interview.
A smarter candidate will figure out you're playing games, which defeats the purpose. I think you also want to consider the reaction of the candidate after the interview. Suppose they answer honestly, then figure out what you did to them.
There's a big difference between trying to learn a prospective employee's motivations the old fashioned way and trying to trick it out of them. Especially when a highly motivated employee can be lowballed in a salary negotiation.