Wouldn't you have to model every class / build to get an accurate picture though? Or is there an underlying pattern that can be used?
At a first iteration, you can assume D&D designers balanced the classes.
So I say we pick one of the easiest classes to model, and work out the characters total HP soak and damage over a "typical adventuring day" (well, "burst damage" and "at-will damage" as two separate values).
Paladin is also easy if we assume they use all their spell slots for smite. They have HP, HD, Lay on Hands, at-will weapon attacks, ASIs that are a bit slower than the fighter, and smites.
The next time I have 20 minutes free with a spreadsheet I'll plot it out.
Wow, just wow. I often create custom mobs (in not reskinned MM mobs) and in most cases I manage to put up a challenging fight and I roll out in the open. But that kind of analysis ...
So I got a little task for you just out of curiosity:
How many mobs of which CR would it need to create a TPK for a level 20 4-man let us say fighter-rogue- cleric-mage party with a 90% probability?
No can do. What I'm doing is analyzing encounter building math. I'm not doing PCs yet.
The point of the encounter building math to me is being able to reliably build encounters with a wide variety of monsters that are reasonably on-target in difficulty, relative to other encounters built differently.
I'm at this point trying to emulate the D&D 5e DMG math, but doing it without having to use their specific awkward system.
So I can build encounters with a Hydra, or a bunch of Barbarians, or some Harpies, or whatever. And they will be in the right ballpark.
I mean, take a published adventure where you fight 10 orcs and an orc chieftan. You drop it into a world where they are no orcs, and want to use a knight and a bunch of guardsmen.
Orc War Chief: CR 4 (36 EBP)
Orcs: CR 1/2 (8 * 10 EPP = 80)
Knight: CR 3 (28 EBP)
Guards: CR 1/8 (3 each)
116 - 28 = 88
88 / 3 =~ 29
So, try using Knight and 29 Guards as a swap in for an Orc War Chief and 10 Orcs. A bit of a pain, but mass Guards can be rolled. (sanity check: Orcs deal almost 2x damage of Guards and are more accurate. They have worse AC, but more HP, which is mostly a wash. Knight is weaker than the War Chief by a reasonable chunk.)
At 116, this is a level 10-11ish medium difficulty encounter.
It isn't the only way to do this, but it is one way. And I find this way really easy, once I get the base math right.
In addition, I can use this to scale an exiting encounter for more/fewer PCs.
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The largest problem with PCs is that individual character optimization levels vary, and classes/builds vary in how much they can "full burn" for the 5 minute adventuring day style. So you'll have to get an idea of what kind of encounters your party can handle over a day. Once you have that, you can get an idea of what difficulty of encounters they can deal with.