I have not found any FindMPI.cmake file (even in MPICH2 or OpenMPI project directories), but only a MPI.cmake file, in <boost-source-root-dir>/tools/build/CMake/externals. There, by adding the following lines, I was successful in building Boost.MPI with OpenMPI rather than with MPICH2:
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set(MPI_INCLUDE_PATH /usr/include/openmpi-x86_64)
set(MPI_COMPILE_FLAGS -I/usr/include/openmpi-x86_64)
set(MPI_LINK_FLAGS -L/usr/lib64/openmpi/lib -L/usr/lib64/openmpi/lib/openmpi -lmpi_cxx -lmpi)
set(MPI_LIBRARIES /usr/lib64/openmpi/lib/libmpi.so /usr/lib64/openmpi/lib/libmpi_cxx.so)
set(MPI_FOUND 1)
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[Note: the file attached is the corresponding patch]
However, you may see that I am not a CMake specialist, and that I have hard-coded the pathes of OpenMPI. So, if some of you know better CMake than I do, do not hesitate to improve OpenMPI detection.
D.