Unfortunately, a couple of answers are sending you via Vermont and Rome 2 Rio hasn’t worked correctly for years. Marseille is two hours east of Montpellier.
I'm sure Nigel, a former railroad employee, is correct on the early morning TGV direct from Colmar.
I took the direct TGV from Strasbourg to Montpellier yesterday. It's first stop is Mulhouse, so you aren't an early riser for Nigel's 7:16 train, you could take the Colmar to Mulhouse train and change to a later TGV to Montpellier. From Montpellier, you'd get a train to Carcassonne. This is the route JoLui has suggested.
It’s long, but lovely looking out the window and going through so many geologically distinctive regions. The train is an old single-level model and gets up to the TGV speeds we are used to from time to time.
A good first stop for you would be Besançon or the capital of Burgundy, Dijon. A second stop could be Montpellier. But if you do it with only one overnight, stop in Lyon. It's all old, stone and highly photographic. Sometimes it's even quaint.
I don’t know anything about your next leg, but if I were doing it, I’d check if I could fly direct flight to Rennes from Toulouse and then decide between train and plane.