In southeastern Tennessee, I'd expect you to be in USDA zone 7 so no worries about soils freezing to any significant depth or anytime soon. So yes, you can go ahead and divide and replant now. Liriope is pretty darn hardy stuff - shouldn't have any problems over winter.

I think Liriope is one of those things that you just cannot kill. :p Example: I once dug some with the intention of replanting, but didn't get around to it right away so it sat in a wheelbarrow for a month or two. I couldn't believe when I found it later and it was still alive!

It's true that liriope can be divided at virtually anytime of the year, even summer, as long as it goes into decent soil and gets regular water until it establishes. However, dividing, if you have to cut/chop the plants apart, tends to ruin the shape of the plant for awhile. If you wait and do it in late winter or very early spring, you could avoid this problem. We typically cut back monkey grass in February, and that would be the ideal time to divide too. As the new growth emerges, it will make the nice neat round shape from the start. If time and opportunity is more important to you, do it now.