No tms are available by pickup from Black and White on. Earthquake Focus punch and rest where available by pickup in emerald, diamond, pearl, and platinum. and earthquake grass knot and Fling where available by pick up in HG and SS.
Source: http://bulbapedia.bulbagarden.net/wiki/Pickup_(Ability)
After generation IV, Pokémon with Pickup can no longer pick up TMs, this is because there is no need to seeing as TMs can be reused beginning in generation V.
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