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Captive bolt would be just as lethal as a bullet, and less messy. They're designed not to make a mess ever since BSE, you don't want to get brains everywhere. Yes that sounds grisly but I run a ranch, it's something we have to talk about.
They could use a custom designed unit, but if the ones we use can drop a full grown bull, I suspect they would be adequate.
A small and fast bullet like .22 Magnum is also extremely effective and leaves no mark except a tiny clean hole, at least on livestock. But they have different skulls from humans. I'm sure those ballistic gel guys could come up with the optimum bullet and load.
I don't know all the details, but more than a few people have survived head shots with small caliber rounds. Captive bolt would certainly be as effective and pretty painless, which really should be the goal if you're considering capital punishment.
Definitely small calibers have terminal performance issues. They lose energy fast at long range, barrel length and weight are critical, quality control is just plain not as good on cheap rimfire ammo. We had a guy in to butcher a batch of lambs for us awhile ago and his .22 misfired over 5 times...
That's why .22 is banned for hunting in most places because while it can easily be deadly, it's not reliably so.
When we do it ourselves I use .22 Magnum even on small animals like lambs because it's MUCH more deadly, it's never failed me.