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The catch can just intercepts oil mist from the valve train....and prevents carbonization of the combustion chamber ....
I guess if yours is carbonized, you clean it and install the catch can that you would have improved HP but it would not provide an improvement over an already clean combustion chamber ... IMHO.....
You can look at it like that I guess.... Its not a hp adder so to speak, BUT, it helps prevent carbon build up on the back of the valve heads, which IS power robbing over time, so yea, I guess you could say it improves power by preventing power stealing oil deposits from building up.
Headers have nothing to do with it as far as I know..
LS engines are notorious for sucking up oil vapor via your PCV system-
GM made several attemps to address this with the later models-
as mentioned no immediate HP gains but in the long run it will prevent carbon build-up and you won't LOSE any HP
Do this---take you Throttle body off---Then get a flashlight and look into your intake manifold---You'll be SHOCKED to see how much oil is in there !!!!!
Easiest fixes are to install a LS6 (Z06) intake valley--newer C5's already have one--only about $75 but it helps alot--Untake manifold has to come off---You'll have to re-route your PCV valve--Then ultimately install a catch can or better yet I like a "coelesating filter assembly--I've had much better success with them over a catch can-- My intake manifold is completly DRY with this set up-I also installed an atmospheric breather (it's illegal smog wise but you can remove/replace it when you go to get it smogged)---My coelesating filter reseivoir will accumulate about 1-2 onces of oil every 2-3 K miles !!! unbelievable how much !!
As was mentioned, the advantage of having a catch can installed is that it prevents gradual HP loss over time. The PCV valve (if part of your engine's emission system) requires oil lubrication in order to function properly but the amount of oil that sails past it is well beyond the very small amount that is necessary.
You can read more about the PCV valve, catch can variations, and a whole lotta other stuff, here: