1) Octane has NOTHING to do with "combustion value."
2) Octane has NOTHING to do with burn rate.
3) Octane has NOTHING to do with amount of additives or agents. Although most brands names DO put in a better quality additive package in their premium fuels. But this is NOT required.
Octane ONLY has to do with the fuels ability to resist detonation. PERIOD.
BTW, in the US we buy fuel by AKI (Anti Knock Index) not by octane, at least since the early 70s. AKI is the average between the RON (Research Octane Number) and the MON (Motor Octane Number). The two are measured using different parameters of things like engine temp, intake air temp, oil temp, etc. MON is a more stringent test and gives lower ratings. There is NO specific relationship between RON and MON. However, in Europe (which puts RON on the pumps), they found that high performance engines run on longer high speed runs had engine failures, even though the RON was proper. But it was found that the fuels that caused this problem had a low MON. So the US AKI rating helps prevent this.
Ethanol does raise the AKI of the fuel, but its main purpose (other than a disguised farm subsidy) is as an oxygenate. MTBE was removed due to concerns over leaking tanks contaminating ground water. So ethanol was proposed as a substitute. The use of oxygenates is to reduce air pollution. It used to be that MTBE was only added to gasoline in the winter. But later, they just added it all the time. Now, ethanol is mandated in most areas for all gasoline.
What you seem to be calling "combustion value" is more typically energy content per volume. In the US BTU per gallon, in metric countries, MJ per liter. There is no specific relationship between AKI and energy of a fuel. Although many higher AKI fuels are lower energy content per volume (alcohols especially).
Some energy content of common fuels (MJ per liter):
Regular gas 47
Premium gas 46
Ethanol 31
Methanol 20
Diesel 48
Vegetable oil 38
Biodiesel 40
Aviation Gasoline 47
As for gas mileage and AKI, everything I have seen, shows that most modern cars get better gas mileage with higher AKI fuel. Typically enough to off set the increased price. But YMMV.

So test in your car, and your driving to see. You will need to keep accurate records, and do it over several tanks to average out differences in driving for various tanks of fuel.
As for additives, all the top brand gasolines have additives to clean injectors and reduce intake valve and combustion chamber deposits. According to several petroleum engineers, they all also leave some deposits of their own. So they recommend switching gasoline brands, not using just one. Being engineers, they do things like switch brands every 2000 or 5000 miles (the time it supposedly take for a given gasoline to remove the existing deposits and start leaving their own). I just switch depending on what is convenient and inexpensive. I DO run high quality name brand gasoline in my good vehicles. Not the convenience store brand or off brand station gas. Many car companies recommend or require Top Tier gasolines.
Info on Top Tier brands, see here:
http://www.toptiergas.com/
Top Tiers brand list:
http://www.toptiergas.com/retailers.html