I like to go 6 to 8 hours on MHs and IMO the LED is pointless in terms of reef inhabitants so I see it as there for our own pleasure...so run it whenever you want.
BTW...I like moon lighting...don't get me wrong, I just don't see much benefit for it on a reef except that it looks cool. ..which is why I have 3 that I run 24/7 because LEDs don't really burn out and you can't see them when the MHs are on anyway so there is no harm.
i.e. shoot for roughly a 10 hour photoperiod with some "tapering" of light at each end. If you can control the three bulbs independently, you can stagger the start/stop times to get some dawn/dusk simulation.
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