I took a glimpse on Hoare Logic in college. What we did was really simple. Most of what I did was proving the correctness of simple programs consisting of while loops, if statements, and sequence of instructions, but nothing more. These methods seem very useful!
Are formal methods used in industry widely?
Are these methods used to prove mission-critical software?
I cannot comment much on mission-critical software, although I know that the avionics industry uses a wide variety of techniques to validate software, including Hoare-style methods.
Formal methods have suffered because early advocates like Edsger Dijkstra insisted that they ought to be used everywhere. Neither the formalisms nor the software support were up to the job. More sensible advocates believe that these methods should be used on problems that are hard. They are not widely used in industry, but adoption is increasing. Probably the greatest inroads have been in the use of formal methods to check safety properties of software. Some of my favorite examples are the SPIN model checker and George Necula's proof-carrying code.
Moving away from practice and into research, Microsoft's Singularity operating-system project is about using formal methods to provide safety guarantees that ordinarily require hardware support. This in turn leads to faster performance and stronger guarantees. For example, in singularity they have proved that if a third-party device driver is allowed into the system (which means basic verification conditions have been proved), then it cannot possibly bring down that whole OS–he worst it can do is hose its own device.
Formal methods are not yet widely used in industry, but they are more widely used than they were 20 years ago, and 20 years from now they will be more widely used still. So you are future-proofed :-)
Polyspace is a a (hideously expensive, but very good) commercial product based on program verification. It's fairly pragmatic, in that it scales up from 'enhanced unit testing that will probably find some bugs' to 'the next three years of your life will be spent showing these 10 files have zero defects'.
It is based more on negative verification ('this program won't corrupt your stack') instead positive verification ('this program will do precisely what these 50 pages of equations say it will').