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1.Prepare the dough: In a medium heatproof bowl, melt the butter and the chocolate together over a pot of barely simmering water. Remove from the heat and let cool slightly.
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2.In a large bowl, whisk together the flour, sugar, cocoa, baking powder, baking soda, and salt.
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3.Add the buttermilk and vanilla to the melted butter mixture and stir to combine. Stir in the egg. Add the wet ingredients to the dry ingredients and stir with a wooden spoon until the mixture is combined. Transfer the dough to a piece of plastic wrap, wrap it well, and let it rest for 30 minutes in the refrigerator.
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4.In a heavy pot with a candy thermometer attached, heat 3 inches of oil to 360u00b0 F. Meanwhile, scoop the dough into 1-tablespoon balls. (A mini ice-cream scoop is a great tool for this.) Roll each ball into a neat circle between the palms of your hands.
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5.Use a spider or a slotted spoon to gently the dough balls into the oil, 4 at a time. You can add a few more balls depending on the size of your pot, but don't crowd the pan. Adjust the flame to maintain the temperature between 350u00b0 F and 360u00b0 F at all times. Cook the dough until puffed and cooked through, 2 to 3 minutes. (Color isn't a good indicator of doneness, so feel free to open up the first or second doughnut to make sure it's cooked through.) Use a slotted spoon to transfer the donuts to a paper towel-lined baking sheet. Repeat with the remaining dough.
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6.Prepare the glaze: In a small bowl, whisk together the confectioners' sugar, milk, and vanilla until smooth. The glaze should be about the consistency of heavy cream. Add a little bit of water if necessary. Dip each donut into the glaze. Use a fork to cover each doughnut, then lift it out and tap it against the edge of the bowl to remove excess glaze. Transfer the glazed donuts to a rack set in rimmed baking sheet. Repeat with the remaining doughnuts. Let the donuts stand until the glaze is no longer wet.
