If their spot is taken by another peep, they end up going to that empty spot on the left side.. or if the rest of the table is full, they'll go to the free spot.
A sound theory, except for my one beloved couple, they are empty nesters, and they still sit next to each other in the same spot. The wife sits at the empty seat, and her husband will sit to her immediate right. They've eaten this way since their wedding day. It's so romantic!
But for most of my couples, when they first marry, one will sit at the empty spot and the other chooses a spot somewhere else - often at the opposite end of the table. I don't know why they like the empty spot so much.