Preheat the oven to 350°F. Line two 8 cake pans with parchment rounds and spray evenly with nonstick cooking spray.
In a small heatproof bowl, whisk together the cocoa powder and espresso powder. Pour the boiling water over mixture and whisk gently until smooth. Set aside to cool completely.
In a large bowl, whisk together the flour, salt, and baking soda. Add brown sugar and use your hands to break up any clumps until the mixture resembles sand.
In a separate small bowl, whisk together the sour cream, oil, eggs, and vanilla until smooth. Make a well in the center of the dry ingredients and pour in the wet ingredients. Starting in the center, use a whisk to slowly pull the dry ingredients into the wet until mostly combined. The batter may be slightly lumpy.
Add the cooled cocoa mixture and whisk until the batter is smooth and evenly combined.
Divide the batter evenly between the prepared pans (about 740 grams per pan). Tap each pan firmly on the counter a few times to pop any air bubbles. Bake for about 32 to 35 minutes, or until a toothpick or cake tester comes out with moist crumbs attached.
Cool in the pans for 30 minutes, then (if needed) run a thin knife around the edges and remove to a wire rack to cool completely.
Make the frosting:
In the bowl of an electric mixer fitted with the paddle attachment, beat the butter and peanut butter on medium-high speed until light and fluffy, about 3 minutes, scraping down the sides and bottom of the bowl as needed. Add the vanilla, salt, powdered sugar, and cream and continue beating until the frosting is smooth and fluffy, about another 3 minutes. Add additional cream to smooth the frosting if needed.
Prepare the ganache topping:
Place the chopped chocolate in a heatproof bowl. Bring the heavy cream to a simmer, then immediately remove from heat and pour over the chocolate. You can also do this in the microwave. Cover for a few minutes then stir until smooth.
Allow to cool until ganache has thickened but is still pourable, about 10-20 minutes. Don’t place ganache in the fridge to cool. Meanwhile, assemble the cake.
Assemble the cake
If your cake layers have domed at all, level with a serrated knife or cake leveler until it is flat for easier assembly.
Place one cake layer on a cake turntable or cake stand. Place strips of parchment paper under the cake to prevent a frosting mess.
Spread a generous, even layer of frosting over the top, pushing it out over the edges slightly. Place the second layer upside down onto the frosting so the top of the cake is nice and flat.
Using an offset spatula, spread the remaining frosting evenly all over the cake, smoothing the edges.
Apply the chocolate topping
Test the consistency of the ganache by pouring a little down the side of a glass. If it’s too thick, microwave for 5 to 10 seconds. If it’s too thin, allow to continue to cool. Spread all over the top of the cake and allow it to drip down the sides. Top with peanut butter cups, if desired.
Serve immediately, or cover and refrigerate for up to 2 days. Let sit at room temperature for an hour before serving.
Notes
1. If you don’t have espresso powder, you can replace both the espressopowder and boiling water with 1 cup hot strong coffee. If you don’t like the taste of coffee or espresso, just use hot water and omit the espresso powder completely.2. If using natural peanut butter, make sure it is extremely well stirred and totally smooth.3. The amount of powdered sugar you’ll need will vary depending on the style of peanut butter you use, as well as the brand of sugar and how humid it is in your kitchen. Start with less and add more to stiffen and sweeten as you desire.
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