Position an oven rack in the center of the oven and preheat to 350 degrees F.
In a large mixing bowl, stir together the cocoa powder, flour, and salt. Set aside.
In a separate bowl, using an electric mixer, cream the butter and sugar until light and fluffy. Add the eggs and beat until thick and lemon-colored, about 2 minutes. Blend in the vanilla and the melted, and cooled chocolate. Slowly add in the cocoa-flour mixture, mixing until combined. Stir in the chocolate chips and pecans, saving some pecans for garnishing the top.
Generously butter and flour a 13 by 9-inch pan. You can also use a 10-inch springform pan. Fill the pan with batter, and dot with pecans.
Bake until a wood pick or skewer inserted in the center comes out moist from the melted chocolate (not batter), about 25 minutes. The top will likely start to show some cracks - it is drier than the interior. Let the brownies cool completely on a wire rack. Cut into 12 squares, or if using a round springform pan, cut into a nice big triangle. Top each brownie with warm caramel sauce, and a small scoop of your favorite vanilla ice cream.
Put the water and sugar in a saucepan over medium heat. Bring the mixture to a bare boil to dissolve the sugar, and then jack up the heat to a full rolling boil, and let it boil away for 20 to 30 minutes, or until brownish. Do not touch it.
As soon as the sugar is medium brown in color, whisk in the cream (carefully, it can splatter). The sugar will clump, but gradually be mixed in to the 'syrup'. Continue to boil until thicker. It will thicken even more as it cools. Season with salt and cayenne pepper. Serve warm on top of the brownie with a scoop of vanilla ice cream