In fission reactions, the concept of the 'cross-section' is important in understanding how likely a particular reaction will occur. For the most common type of uranium fission reaction, U-235, this isotope is likely to fission when the uranium nucleus is struck by a neutron have a certain minimum energy, whereas, if a U-238 nucleus were struck by a neutron with the same energy, no fission reaction would occur. In a hydrogen bomb, the fusion reactions produce much more energetic neutrons, which, when they strike U-238 nuclei, cause this isotope to fission.
For the early hydrogen weapons tests, cryogenically stored deuterium was used as the fusion fuel, but this meant the weapon weighed many tons and was impractical to deliver in a combat situation. The development of the so-called 'dry' fusion weapons required that the deuterium fuel be compounded chemically with another element which would not inhibit fusion reactions and which would keep the weight of the device to a minimum and be chemically stable at room temperature for a long time.
When it was decided that lithium was the ideal choice to compound with deuterium, physicists thought that the Li-6 isotope would fuse readily given the conditions produced by detonating the primary. There was a program to separate Li-6 from the more common Li-7 isotope, much in the same way that U-235 was separated from U-238. In the first test of a lithium-deuteride device, the lithium-6 isotope had been enriched from the natural 7.5% to approx. 40%.
http://en.wikipedia.org/wiki/Castle_Bravo
The reactions occurring in the lithium were poorly understood when this device was designed and tested, which was why the extra yield came as a big surprise to the observers at the test site. In analyzing the results of the test to figure out why the device had such a greater yield, it was discovered that Li-7, rather than remaining inert, can actually capture very energetic neutrons, like the type produced in a fusion blast, and then decay into an alpha particle, a tritium nucleus, and emit another neutron. The tritium is additional fuel which can fuse during the detonation, and the neutron, being quite energetic, can go on to cause additional fission reactions in the U-238 tamper.
The original designers had overlooked the fact that while Li-7 has a very small 'cross-section' for the neutrons emitted in the fission blast, once the more energetic neutrons from the fusion reactions start to be produced, the 'cross-section' of Li-7 is much larger, and this isotope is more likely to capture and react with these energetic neutrons. The designers' lack of understanding on this point can be understood, since Castle Bravo was only the second H-bomb test but the first to use lithium-deuteride as the fuel.
This was an important discovery since a.) it meant that isotope separation of lithium into Li-6 and Li-7 would not be required, causing a considerable saving in time and money when it came to mass-producing hydrogen weapons, and b.) each weapon could be smaller for a given yield than originally thought, due to the extra energy which the Li-7 reactions would produce during detonation.