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That is the answer to your question. To spell it out :-), there would be no constitution of the United States of America if there were no states. If a state left the union, it was up to the executive branch to decide on a course of action and the legislative branch to ratify or reject that course of action. AS SOON AS STATES LEFT THE UNION THEY WERE, BY DEFINITION, NO LONGER PART OF THE UNION. the remaining states had to decide how to respond to this threat to their sovereignty. This was done constitutionally by the states remaining in the union. Fortunately for the seceding states, the UNITED STATES decided to go to war with the newly established government of the confederacy to challenge its legitimacy. The rest is history.

There is nothing in the US Constitution that says you cannot leave the Republic. The actions of the remaining States speaks volumes. It kind of reminds me of the movie Godfather III. You cannot ever leave or there will be bloodshed. Nice....