With necromancer charming for pure xp, you're mostly looking to have you charmed pet take as much damage as possible, break charm, and kill it with 1 cast of say, deflux to get xp. So you send your pet against 2-3+ other mobs if possible (1v1 is a must in some scenarios). And you cycle rooting those mobs on top of each other. Once your mobs low you use clicky invis (normally pre-nerf Circlet of Shadows), and break your pet low, and deflux. Rinse and repeat. You don't really care much about -MR at all cause if charm is breaking frequently you're probably attempting too high lvl of mobs for your lvl, and your pet should die fast to the other mobs.
It's a mix of charming and root rotting to help keep mobs around the same amounts of health if they vary in level. You're not charm xping solo the most effective way as a necro if you're trying to keep 1 mob charmed the entire time to beat down another, that's not nearly as effective, let NPCs be your DPS, not your charmed pet.
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