If VT and UVA are not in the same pod, which is likely
for a couple of different reasons, then there is always the possibility that VT's pod and UVA's pod may not be paired together. Given how important access to the southeast states for recruiting purposes is (among other reasons), then it is unlikely there will be enough schools to support quads being broken out like this:
I do agree that the 4 NC schools are the most likely candidates to be upset with majority of the suggestions, but I wouldn't completely rule out a non-NC school being more upset because it may depend on whether the ACC has 2 quads with 2 NC schools or 4 quads with 1 NC school. Personally, I think the ACC will lean towards the 4 quads with 1 NC school option because it will make it easier to ensure that each quad has 1 school from Quad 4 in the above example.
One reason I asked whether you would be okay with not playing UVA every year is because I could see a scenario where ESPN wants certain quads paired together so the football schools play each other more frequently and help increase the quality of content. So it is possible that ESPN/ACC decide that balancing out the quads with the "football" schools is more important than the UVA-VT rivalry in football. The quads could end up looking something like this (assume 1-2 and 3-4 are paired together):
In this scenario each quad has 2 quality football schools (FSU, Louisville, Miami, UNC, Clemson, WVU, VT, and Notre Dame). Also, each quad would have 1 historically bad program (Syracuse, UVA, NC State/Pitt, and Wake). It is also possible that the UVA-VT annual rivalry may be sacrificed so 1 quad doesn't end up with 3 quality "football" programs (i.e. Clemson, Louisville, Miami).