Would being able to be a Good assassin mess up the game or something? Have the designers ever explicitly stated why they added that requirement to the class?
Secondly, is there an alternative?
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There are a lot of character options that have plot/alignment based restrictions. Almost all can be ignored by DM fiat, and many only apply to a very specific campaign world that you may or may not be using.
Many races have alignment restrictions, which is, lets be honest, a tad racist. Fantasy is full of examples of non-evil goblins (World of Warcraft), Ogres (Shrek) and Vampires (Team Edward!)
Classes also have some unnecessary restrictions. While most Barbarians will be chaotic, there is nothing to prevent a DM from creating a world where barbarians form tight-knit tribes of lawful aligned individuals. Arguably the Aiel in the Wheel of Time series would be significantly comprised of barbarians (and scouts, rangers), but they are certainly lawful aligned.
Paladins originally had lawful good as a restriction. That was later expanded to any of the 4 extremes with minor changes to abilities.
Other people have recommended doing away with alignment (restrictions). I would recommend keeping them, but adapting them to your campaign world.
Don't ask "is there any reason why I shouldn't allow a good assassin", instead ask "if there is a good assassin, who trained him?" Is there a good assassins guild? (avenger/slayer of domiel style). Or was the character once evil, trained with evil assassins and has since had a change of heart? If so, it's probably that the assassin's guild wants him dead, as do the various relatives of his innocent victims. I smell a side quest.
Don't worry about whether dropping alignment restrictions will impact the rules, but will it conflict with your plot?
In the Dungeon Master’s Guide, the assassin prestige class isn’t just for someone who kills for hire, but rather quite specifically for a member of a (fairly generic) “Assassin’s Guild,” and that guild requires that you kill someone for no other reason than to enter the guild as part of its initiation. That right there is a pretty Evil act, and the organization as a whole is Evil. If you maintain this organization and its initiation rites, and all members of the assassin class are also members of this organization, the alignment requirement makes... about as much sense as an alignment requirement ever does.
If you don’t have the organization or its initiation rite, there’s really no reason at all; the assassin class kills people, but all of the classes do that. There’s nothing extra-special evil about the class. The name implies that you kill for money... but even if you do, killing for money is hardly uncommon among the adventuring type. Plus, you don’t have to, and all of the classes can (well, except maybe paladin).
I am not aware of any external developer commentary on this point, however.
There are at least two classes that are similar to the assassin, and can be or must be Good.
The avenger prestige class is almost identical to the assassin, changing only a little of the flavor of the class, and the alignment and special requirements. The avenger spell list is different, but only slightly compared to the Core assassin spell list. Additional assassin spells (such as from Spell Compendium) should be added to the avenger spell list.
The avenger is pretty solid evidence that losing the Evil requirement causes no mechanical problems for the assassin.
Note, however, that the avenger was actually posted as an April Fool’s Day joke. This may indicate what Wizards thought of the idea of a Good-aligned assassin... but more likely just speaks to the idiosyncrasies of Creighton Broadhurst, the author, since web articles did not receive much attention from editors.
The slayer of Domiel from the Book of Exalted Deeds must be Lawful Good, and get their power from Domiel, a powerful archon. They don’t use poison, and their spell list is different, but they are still “assassins” in terms of what they do, and they still have Death Attack. The Book of Exalted Deeds spent a lot of time decrying “evil” tactics (poison, mind rape), and offering alternatives – that did the exact same thing, just with the Evil serial numbers filed off (ravages, sanctify the wicked). It is not well-written book.
Still, the slayer of Domiel is, again, solid evidence that there isn’t an inherent, systematic problem with Good assassins. The slayer of Domiel itself is a thoroughly mediocre class, even compared to the assassin, and I don’t recommend it, but its existence should be comforting for those who want to waive the requirements on the actual assassin.
There is no mechanical need for the alignment or special requirements on the assassin class. I have run or played in several games that had characters with levels in the class who were not Evil and had never killed someone to enter; it was never a problem.
In fact, in general, in most of the games I play or run, we have eliminated alignment entirely. There are a few problems with this, but they can be handled. I tend to think this is better for the game:
Basically, alignment is legacy content from a game designed for dungeon-delving and dragon-slaying, and little more; as the genre and the game have grown, developed, and matured, alignment has stayed more-or-less the same. Originally, the heroes were Good because they were the heroes, the villains were Evil because they were the villains, and everyone else was Neutral because they were ignored. The elf was Chaotic cuz he was an elf, and the dwarf was Lawful cuz she was the dwarf. That’s about as far as it went, and that’s close to as far as it can go. Modern games of D&D are typically much more detailed, much more nuanced, and characters are much deeper; they no longer fit in nine neat little boxes, if they ever did.
For more on eliminating alignment altogether, I recommend this answer.
Mechanically speaking, there is no problem. Other than potentially the requirement of having to kill someone for no reason, which is hard for a Good or Neutral person to meet. (But can easily be waived as well)
Classes are generally balanced around their mechanics and there is no "extra power" granted for alignment restrictions. In fact, many classes with an alignment restriction are pretty bad, the Druid being a notable exception.
I'm not sure why the requirement was added, but I'm guessing because the designers felt that a character who sneaks around and murders people from the shadows isn't something they want as a player character? But then, the Rogue is in the PHB so it always felt a bit silly and contrived to me.
So there should be no problem if you remove it. The idea of alignment restrictions has been abolished in later versions of D&D, you could easily play a Good aligned 4e Assassin and I've never heard of anyone having problems with it from a flavor point.
I even read (after looking for some alternatives) on a forum that WotC actually ran the good aligned assassin as an april 1st joke, renaming it the Avenger and just changing the alignment restriction, and nobody seemed to have any problems with it. Unfortunately, I cannot find the actual article anymore. But if your joke is taking at face value and still not found problematic, you can be reasonably sure that the alignment restriction does nothing.