I *think* this is correct but I want to double check.
If I get myself a scroll of Faerie Fire, can I use it with UMD by pretending to be a Mesmerist, that has FF on its list, but thereby only needing to have a high Cha score rather than a high Wis score?
My understanding is that spells on scrolls do not have a particular class hard-coded into them.
Otherwise, presumably, I could buy a Mesmerist FF scroll.
FF is on the Mesmerist spell list, so you can get a psychic scroll made with that spell which you then cast using CHA as the stat.
I think that broadly speaking as long as you are buying the scroll yourself, you can probably always find a CHA based caster that can cast any spell.
Which is most optimal for UMD, since you're likely to have a reasonable CHA just to use the skill.
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If you can find a psychic scroll of faerie fire, you're good to go. Not so much if it's a divine scroll unless Paizo prints a Charisma-based casting class with faerie fire on its spell list.
Re: "broadly speaking", there are plenty of spells you may not be able to find on psychic scrolls simply because they don't appear on psychic class spell lists. While you can cover a lot with non-psychic classes that have archetypes that make their spells psychic (e.g., psychic bloodline sorcerer, which doesn't really matter here as sorcerer is already Charisma-based), in a lot of settings characters with such archetypes that also happen to create scrolls for sale may be rare enough to make finding such a supplier an adventure in and of itself. In other settings, they might be readily available.
TL;DR: Find a class whose magic type corresponds to that of the scroll (arcane, divine, psychic) and uses Charisma as a casting stat. If you can, UMD it and you're good to go.
If you are investing in UMD, you probably can also emulate the casting stat.
Use a scroll: 20 + CL
Fake a stat: 15 + Stat
Given that WIS affects saves, you probably do not want a negative mod here. Getting a +2 item (even an ioun stone) can cover you for low level spell needs. Likewise, INT affects skills, if you are a caster, you don't really want this to be negative either. If you go for sorcerer/oracle class lists, you use CHA which also feeds UMD.
If the UMD fails, they can retry later. If the UMD fails and was a 1 on the d20, they cannot try for a day. There is no Scroll Mishap in the UMD rules.