Ideally, a person is continuously weighing risks. In rare instances, there is a round in the chamber, when I hunt. The terrain must and footing must be decent enough that the risk of slips, trips, or falls are minimal. Also, there has to be a strong hunch that an animal is close by, and the shot will likely be fleeting.
The best mule deer I killed was taken with a round in the chamber, before I saw him. I was alone, and still hunting a timbered ridgeline that was oozing with sign. I came to a spot, where the terrain leveled out, and there was an even greater concentration of sign. After I put a round in the chamber, it wasn't more than a minute, before he rose out of his bed. If the footing had still been as steeply side hilling, I would not have had a round in the chamber. If I had not come across the buck, and the terrain again became steep, the round would have been taken out.
Many years ago, I drew a moose tag, and took my young son with me on a scouting trip. I remember telling him to always realize we were a long way away from medical help. Given that, we should factor that into everything we do, on the mountain.