No, not pouring, it is a gel and the only way to get it to smooth out is to wait till a film comes on it and smooth it out with the fingers.
The active ingredient in silicone caulk is acetic acid which leaves the caulk and causes it to harden, it actually needs a damp environment to cure.
It can however take up to 2-3 days to cure and up to a week with thick walled molds, so the best thing to do is by spraying the caulk with water and then going over it with a hair dryer, it will aid the evaporation of the acetic acid.
