Pump a few bullets into someone who's running at you and then throw knife. This usually works. The go down like a sack of turnips!
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I think that if you're good / lucky enough to get a throwing knife headshot in PVP, it should be a kill straight up. I mean, the Titans get that with a simple shoulder charge. Although won't really complain when Golden Gun shoots a fist of havoc or novabomb out of the air!
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If a Titan or Warlock times there Super just right a GG shot wont kill them, Ive lost to a Titan Smash and Warlock Nova because of that split second.
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it takes two GG shots to kill a titan using FoH.
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Thats what I do.. but half of the time the knife will do damage and the dot won't work, or, Ill hit a crit on a full health enemy and the dot wont work. I know how to use the throwing knife, it doesn't always do what its supposed to.
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Just luck for me I guess? There is a perk for an extra throwing knife however.