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the smite enchantment in minecraft makes it so your sword does extra damage do zombies, skeletons and pigmen.
If you're talking about the smite enchantment, then no. Smite affects Zombies and Skeletons.
Smite increases damage against zombies, skeletons and zombie pigmen.
It makes the sword stronger against undead foes
To smite (kill) another player, you first have to be in melee range of them. Then simply attack them by left clicking until they die.