Clearly there's some Heisenberg uncertainty principle where the pawn occupies both the third (or sixth) and fourth (or fifth) rank, in a kind of superposition that only an opponent pawn situated in a certain position would be able to observe.
I think the logic is based on pragmatism. A different piece has a chance of capturing the pawn later, but a pawn would never be able to since it can't go backwards.
It's just it's own unique rule, born from a period of transition between pawns only being able to take one step and being able to take two.