Let's say you put tiny spots of the cloth side of a piece of velcro on a lot of ping pong balls, and tiny spots of the hook side on a lot more ping pong balls, then you let them bounce around a room at enormous velocities and see which ones stick together. That would be your intermolecular binding.
If you attach some of the ping pong balls with the cloth side to others with the hook side by a short piece of string, would you expect the ones with the string to be more or less likely to be attached together than to be attached to any of the other wandering ping pong balls? How about if instead of a string, they were attached together by a curved spring that held them so the two patches were facing each other and only a few millimeters apart? That would be your intramolecular binding. The probe is located close enough to the corresponding binding site that the binding site is much more likely to find the probe than the template, which is on a separate stretch of DNA.