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Personally I would recommend starting with Human Action by Mises as it represents essentially the purest distillation of that school of thought and the culmination of a lot of Mises' earlier works. Rothbard studied under Mises so it would serve as a good introduction to him as well.

I highly recommend Rothbard's Anatomy of the State as an excellent starting place. It's really short, practically a pamphlet.

At the end of the day, when it comes to Ludwig von Mises, it's a question of whether or not you believe humans have free will. If you've studied long enough to become a neurologist, you find that free will is laughable.

Do people that have studied long enough to become a neurologist, find this laughable out of their own free will?