These sorts of things are incredibly difficult to get right.
Punished for being proactive?
Some of us have already been proactive. I am a high user, but now have solar and battery. The hot tub (a big chunk of usage) is now on a timer so largely heating in the middle of the night, and easy to avoid the 4-7pm peak. I am also on a special battery tariff, so for example, my usage 4pm-7pm is actually about -30% of my daily usage (yes MINUS 30%, i.e. I export around 30% of my net daily usage 4-7pm).
Now, this means it would be physically impossible for me to use less 4pm-7pm, whether net (i.e. allowing for export) or just import (i.e. currently 0kWh usage).
So no way I can benefit from the Octopus scheme as I see it, unless I have misunderstood, as I cannot "improve" my peak usage.
Had I *not* been proactive. Had I left the hot tub on 4-7pm. Had I not run the battery like this. I could be easily making that extra £100 on offer. I am being punished for my being considerate and proactive - or so it seems. That feels wrong, somehow.
Other approaches
My understanding is that some providers are working on getting people to make their 4-7pm usage a lower percentage of their net 24/7 usage. That would work for me, as I already do that, assuming they would even cope with a negative percentage, maybe I would get more than £100, LOL.
Encouraging bad behaviour
I need to work out the "reference" period for saving. Even on the tariff I am on, it would not be hard to make my 4-7pm usage really high. It would not be hard for anyone to do that by running the washing mashing, and tumble drier (and I know most people don't have one, a hot tub), even electric water heating as many have that as a backup for gas. And, of course, if you have one (we don't) charging your EV.
If doing that for a few days before, then during the key days you move the power usage away from 4-7pm, you can get that bonus. For a lot of people "moving" the power usage has not extra cost, so why not.
This is a problem with any system that is "relative improvement". Make it absolute, e.g. usage below X kWh for the period per hours, or even less than % of net 24/7 household usage, and that may work, no need to force a high "reference" against which you are saving.
Not in the spirit of the scheme
One criticism of anyone adjusting their usage before these saving sessions to get a better reduction is that it would not be in the spirit of the scheme. Not "the right thing to do". Even Octopus said that on twitter.
Well yes, that is true, but the whole scheme is based on people doing "what makes them money" not "what is the right thing". There would be no need for any financial reward if people would "do the right thing", so yeh, you kind of have to expect that people, as a whole, will do what makes/saves them the most money - that is how people as a whole tend to work, even if individuals do sometimes do the right thing - it's the very basis of economics (from what I remember).