Hey clammer,
There is no reason you can't mix your water in the tank while it is empty. I have done this several times, however there are a few pros and cons to doing this.
1st lets talk about the pros- Its easy, the need to bucket water is cancelled.
If the water is not "dead on" you can make adjustments by adding more salt or more RO water right into the tank. Also before you add the salt it is a great time to test all your plumbing for leaks and flow.
Cons- You have to be careful about the volumn of water you mix. This is due to the fact that when you add LR or sand it will displace the water and it is difficult to determine the amount of displacement due to the fact that the rock is very porous. Also it can be messy when adding the sand. When doing aquascaping you will get wet, and it is sometimes harder to put things exactly how or where you like.
There is no "rule" to mixing the water in an empty tank, it is really a preferrence. I have done it both ways and IMO water first is a good way to go. You just have to be happy with getting wet!
Moby