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I've read D&D 3.5 core books and haven't found anything useful in such a scenario - a player is approaching an unaware opponent (for instance with a dagger) and is trying to kill him by cutting his throat. Is there any specific rule on that? I suppose it would be weird to initiate a normal combat in such conditions.

I know the Rogue's Sneak Attack, but what with other classes? And even with this very ability it just adds some additional damage, but, correct me if I'm wrong, cannot kill the target instantly.

Can you recommend me any book containing rules for such encounters or help me find an appropriate rule in any of the core books (I'm interested in RAW rules in the first place)?

Thank you very much for your help and sorry for troubling you if I overlooked something.

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Regrettably there are no general rules for this, but there are some character builds which can do it.

As a fan of Metal Gear Solid I have long lamented that D&D doesn't have a general rule for insta-killing an unaware opponent, but it just doesn't fit well into D&D's ruleset. There are a few circumstances where what you describe is possible:

  • Your opponent is not only unaware, but helpless, defined in the rules as "bound, sleeping, paralyzed, unconscious, or otherwise at your mercy". Against a helpless opponent you can perform a coup de grace attack which automatically hits, deals damage as a critical hit and forcing a Fortitude save-or-die. It's an instant kill but your opponent has to be absolutely unable to defend themself.
  • You're fighting low-level opponents such that your base damage is enough to easily kill them. Most town guards and the like are probably level 1 or 2 warriors, although many DMs don't bother to use such easy challenges when the characters are high level.

A few individual character builds, classes, items or the like allow a melee character to make an instant kill. A few include:

  • A knife smeared with a particularly potent poison can deal an absurd amount of Constitution damage in one hit, causing instant death; however, poison like this is expensive
  • The assassin (Dungeon Master's Guide) can make a death attack which instantly kills an opponent,, although it takes three rounds of preparation to pull off
  • A rogue built for optimal damage might deal enough sneak attack damage to, in practice, kill weaker enemies outright in a single good hit
  • The Mortal Hunter prestige class (BoVD 64) can instantly kill an opponent with a touch once per day at level 10 of the class
  • The Wand of Orcus instantly kills anyone it touches, but unfortunately it's a rare artifact
  • You are of a race or class or are using some item or spell to give yourself a paralyzing touch (lich is a good example), allowing you to instantly kill them on a subsequent round
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    \$\begingroup\$ For the record, the assassin is not the only source of death attack. This link has a probably-complete list. Notable options include binder with Marchosias, King of Killers (ECL 13th, Cha-based, can also get −4 to enemy saves), dark pilgrim of Takhisis (ECL 10th, Wis-based), deathstalker of Bhaal (ECL 6th, much quicker DC improvement), and marrulurk (a race, ECL 4th, and Cha-based). Bone knight gets a 1/day preparation-less “death strike,” and bone knight is a good class anyway. \$\endgroup\$ – KRyan Nov 11 '18 at 0:43

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