Preheat oven to 350º. Line a baking pan with parchment paper.
In a large microwave bowl, add chopped chocolate and butter and microwave on medium power until the chocolate has melted. About 2 minutes, whisking every 30 seconds.
In a separate bowl, combine the flour, salt, and cayenne pepper. Set aside.
Add cocoa powder and sugar to the chocolate mixture and whisk to combine, it will be thick. Add eggs and vanilla and whisk until smooth. Gently fold in the flour being careful not to overmix. Fold in chopped pecans.
Bake for 25-30 minutes, until the edges just begin to pull away from the sides of the pan and the top is set and shiny. A toothpick may have a few crumbs but should not be dripping.
In a large microwave safe bowl, add the chocolate, evaporated milk, and butter. Microwave on medium high for 1-2 minutes, whisking every 30 seconds until the chocolate has melted. Add the powdered sugar and vanilla and beat with a hand mixer until creamy and smooth.
Remove the brownies from the oven and immediately place a single layer of marshmallows over the top and return to the oven for 2 minutes to let the marshmallows soften.
Remove and drizzle the frosting over the top while still hot. As the frosting warms up, it will be spreadable. Use an offset spatula to spread it evenly over the marshmallows. Let sit until completely cool before cutting, about 2 hours.