Line a 9×13-inch metal pan with parchment, leaving overhang on two sides for easy lifting. Preheat the oven to 325°F (165°C).
In a large bowl, whisk the warm melted butter with the brown sugar and granulated sugar until glossy and combined, about 1 minute. Let the mixture stand for 5 minutes, then whisk again for 30 seconds to help dissolve the sugars.
Whisk in the vanilla. Add the eggs one at a time, whisking well after each addition, then whisk in the egg yolk until the mixture is thick and shiny.
In a separate bowl, sift together the flour, cocoa powder, cornstarch, baking soda, salt, and espresso powder. Add half of the dry mixture to the wet ingredients and fold with a spatula. Add the remaining dry ingredients and fold just until a few dry streaks remain.
Fold in the chocolate chips until evenly distributed. Scrape the thick dough into the prepared pan and press into an even layer with a spatula or damp fingertips.
Refrigerate the filled pan for 20 minutes to help the bars bake with clean edges and a fudgy center.
Bake at 325°F for 24 to 28 minutes, rotating the pan once halfway. The edges should look set and the center should appear slightly soft; it will firm up as it cools.
Cool completely in the pan on a rack, about 1 hour. Use the parchment overhang to lift out, then slice into 24 bars. For the cleanest cuts, wipe the knife between slices.