Nice line of questions you give here!
Fill the chamber, forget the barrel diameter. If you get a mold from me, I normally cut the first drive band close as I can hold to the barrels groove diameter and the rest of the body large enough so loaded rounds just slip in easily. The bullets can't tip on takeoff with this setup, and bullets should be hard, not the traditional soft tin lead.
For all practical purposes, the barrel diameter doesn't change with heat, because the above set up is way over groove anyhow, so a few 100 thousandths inch of heat change aren't a factor.
Get the LBT lap kit and lap the bore. It will make a precision machine out of your Pedersoli.