I don't think it represents a real event. I think it is intended to represent a whole lot of Tennessee football history from the period of the 70s, 80s, and perhaps even 90s.
The opposing team uniform is clearly Bama. Because, you know, Third Saturday in October--our #1 rival, particularly in that period.
But the player represented is both Hershel Walker (#34 and name on back of jersey) and some other fellow from some other team, #14. No idea who the latter would be.
The Vols could be:
-- #44 -- Bobby Majors
-- #45 -- Johnny Majors
-- #54 -- Bob Johnson, or Dale Jones perhaps
-- #16 -- Peyton Manning, if the painting was painted that late
In short, the painter didn't sit down with a photo in front of him and recreate it. He closed his eyes, saw an event like a goal line stand, and filled in the jerseys with the #s of some players he really respected (both our guys and the opponents').
That's my guess.