New England was making noise about secession during Jefferson’s Presidency, and continued making it until near the end of the war of 1812.
But they didn't, did they?
This was nearly universally denounced as treason at the time and spelled the end of the Federalist Party.
Everyone in 1860-61 recognized secession as Revolution that would require war. The Confederates were eager for a war that they thought they could win, along with their European and Latin American allies.