Preheat the oven to 350°F Butter and flour an 11x15x2-inch metal baking pan or spray with baking spray. Set aside. [Tip: A smaller 13 x 9 inch pan won't hold the batter, toppings and icing.]
Mix together the hot water and cocoa powder until dissolved. Set aside.
Melt chocolate chips with heavy cream in a microwave safe bowl using the melt function stirring until completely smooth.
Cake Batter: In a large mixing bowl using an electric mixer, cream together butter, granulated sugar, brown sugar and vanilla extract. Cream for 2-3 minutes until fully combined. Add eggs one at a time stopping to scrape the bowl periodically.
Add the cocoa mixture to the mixing bowl. Continue to beat for another 1-2 minutes until the ingredients are combined.
In a medium bowl use a whisk to sift together the flour, baking soda and salt. Add to the mixing bowl alternatively with the buttermilk.
Add the melted semi-sweet chocolate. Beat the batter for 1-2 minutes stopping scrape the sides of the bowl periodically.
Pour batter into prepared cake pan. Spread evenly.
Bake for 30-35 minutes or until a toothpick inserted into the middle shows moist crumbs.
Remove from the oven and immediately arrange mini marshmallows on top. Return to the oven for 1-2 minutes to allow the marshmallows to soften. Sprinkle with pecans reserving 1/4 cup for garnishing. Set aside while you prepare icing.
Chocolate Icing: Melt butter, heavy cream and cocoa together in a saucepan over medium-low. Melt just until smooth. Remove from heat and add vanilla extract. Mix well.
Use an electric mixer on medium-low speed to gradually add powdered sugar. Add more cream to thin until it reaches drizzle consistency, if needed.
Pour warm icing over marshmallows and pecans. Sprinkle finely chopped pecans on top to garnish. Set aside to cool.
To Toast the Pecans. Spread the pecans on a baking sheet in a single layer. Toast in a preheated 350°F oven for 6-8 minutes.