I had always been told that the bees, upon sensing smoke in the hive, would think that their tree was on fire and would gorge themselves with honey in preparation for departure. Bees full of honey don't seem to be inclined to sting, which is helpful for the beekeeper.
However, another alternative theory came to mind the other day whilst I was working the bees without the aid of smoke. Upon opening the occasional temperamental hive, a handful of ornery guard bees would pounce, and the powerful odor of ripe bananas would permeate the air. This odor is the bees' alarm pheromone, and it is quite alarming for both the bees and the beekeeper. I realized that while being very familiar with irritable bees and their odors, I had never noticed the odor quite as powerful as it was now. It reminded me of the smell of goldenrod nectar near the beehives in the Fall, very strong and ripe. And so it occurred to me that perhaps the odor is always present when opening angry hives, but the usual cloud of smoke accompanying the opening masks the presence of the odor from both the beekeeper and the bees. The guard bees emit the alarm pheromone, but no one notices.
Meanwhile, those bees that we see gorging themselves on honey may just be cleaning up the mess we've made by opening the hive.
There are alternative methods of calming bees without the use of smoke. No smoke, as mentioned above, works well with very gentle bees, but not so well with the rest of them. I've tried spraying the bees with sugar water while working them, which worked well with gentle hives, but was next to useless with the mean hives.