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Once you're done with Strictly Business, you'll have the opportunity to just go out on your own. Grouse will continue to sell you mesmetron ammo and slave collars. You can use the mesmetron to enslave a number of general NPCs throughout the wasteland. There are some that just can't be enslaved though. You should probably save before you try, so that you don't waste ammo.
It seems like there's a 50% chance for some NPCs to go into the stupor that allows you to put the slave collar on them. There's also a chance that their head will explode or that they will go crazy and fight everyone. The ones that can't be captured have the 50% chance for enslavement transferred to head explosion. So, if someone's head just keeps exploding when you use the mesmetron, then they probably can't be enslaved.
Otherwise, it's all up to you. It does seem possible to use it on some raiders and even enclave soldiers. It's naturally a bit difficult though. It's best use is stealthy work on the general citizens of the wasteland.
It's a decent source of income and a good challenge for role playing. Other than that, you're basically free to do what you want.