Why do you need a second program on the same computer or in your account? The Desktop program can prepare unlimited returns and efile 5 for free. And you can use any version. All the desktop programs have the same forms. You just get more held in the higher versions.
But you can activate a second program. Under Help - Switch Product - Activate new product. Don't know what that will do or what benefit you will get. Don't think it will allow you to efile more than 5 or get a different free state program.
Or explain more what you are trying to do?