There's no exact science because there's just too many variables involved ... not the least of which is your personal physiology and tolerance levels to high partial pressures of O2. It's much like how N2 exposure can lead to DCS in that there's a graduated "gray area" wherein the farther past a certain arbitrary limit you go the higher your risks become of having a bad outcome, based on several other factors. But that doesn't mean you WILL have it. Also, exposure time and differential changes factor into how much risk you're actually taking.
A few weeks back on a solo dive on a wall in Browning Pass I accidentally dropped my camera. I was at a depth of about 80 feet at the time, on a wall with a hard bottom at over 200 feet. I quickly swam down to retrieve my camera, which was sinking, and caught up to it at around 140 feet. As soon as I retrieved it I began my swim back up at a fairly expeditious pace, and slowed down when I got to about 100 feet ... well within the MOD of the EAN32 I was breathing at the time. Yes, I went well below the MOD for the mix I was diving ... but the effects that lead to ox tox are cumulative, and I figured the risks of less than a minute below the "safe" depth were worth taking, considering I was otherwise going to lose about $5000 worth of equipment.
One always needs to factor risk mitigation into any dive ... but it helps to have at least a basic understanding of why PPO2 limits exist, and what it really means if you should need to exceed them in a given circumstance. Of course, it's always better to not have to make that choice ... but sometimes sh!t happens ...
... Bob (Grateful Diver)