Grease the entire inside (including the tube) of a 9 inch diameter tube pan at least 2-3/4 inches tall. Line the bottom with a circle of wax paper cut to fit, grease the paper, and dust the entire inside of the pan lightly with flour, knocking out any excess. Set aside. Adjust rack to center of oven; preheat oven to 325 degrees F.
Place finely chopped chocolate in small microwaveable bowl; add about half of hot water. Allow to stand for about a minute, then stir or whisk until smooth (if necessary, place bowl of chocolate in microwave at medium (50%) power for a short interval, then stir or whisk well until smooth). Gradually add remaining hot water and set aside to cool. Into a medium bowl, sift together cake flour, Dutch process cocoa powder, baking powder, and salt; set aside.
In large bowl of electric mixer (fitted with paddle beater if available), combine softened butter, sugar, and vanilla. Beat at medium speed (speed 4 on my KitchenAid) for three full minutes, stopping once to scrape down bowl and beater(s) with a rubber spatula. At a low speed, add eggs, one at a time. It is important to scrape down the bowl and beater(s) after the addition of every two or three eggs. Adding the eggs will seem to curdle the batter, but don't worry about it now. When all eggs have been added, increase speed to medium again and beat for one full minute (this should smooth out the batter a bit).
Add the rum or crème de cacao to the melted chocolate-water mixture; set aside briefly. Add half of the sifted dry ingredients to the batter in the mixing bowl; blend at a low speed until incorporated. Add chocolate-liqueur mixture, which may be slightly warm or cooled to room temperature; beat in at a low speed until incorporated. Scrape down mixer bowl and beater(s). Add remaining sifted dry ingredients and beat in at a low speed just until incorporated; you might want to use a sturdy whisk to incorporate the last of the dry ingredients and make sure there are no lumps in this heavy batter. Sometimes, the batter still looks a little curdled at this stage, but it should bake up fine.
Turn batter into prepared pan. Spread level. With back of large spoon, form a slight "trench" around center of batter, pushing it slightly higher at edges and onto tube. Place in preheated oven.
Bake 50 to 60 minutes, turning cake back-to-front once after about 30 minutes of baking time. Cake will rise and develop deep cracks on top while baking. As top crust is heavy, test for doneness by inserting toothpick into center of cake in one of the cracks. Cake is done when toothpick emerges with only a few moist crumbs still clinging to it; do not overbake!
Remove to cooling rack. Cool 10 to 15 minutes, then loosen cake gently from pan edges and tube. Carefully invert onto second rack, remove pan, peel off wax paper circle, and re-invert to cool right side up. Cool completely before serving or storing.
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