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I've been playing with and/or against Darmanitan in Pokémon White 2 for a while, and I've never seen Darmanitan change into Zen Mode. Was it introduced in Generation VI?

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Darmanitan's zen mode was introduced in gen 5 as a hidden ability. You can catch it after you complete the main story by using rage candy bar on statues.

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Darmanitan has zen mode in gen 5

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