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1. To caramelize sugar, in a heavy medium skillet melt the 2/3 cup sugar over medium-high heat. Do not stir sugar; shake the skillet occasionally. When the sugar starts to melt, reduce heat to low. Cook, stirring frequently with a wooden spoon until sugar is golden brown.
2. Remove the skillet from heat and immediately pour the caramelized sugar into four ungreased 6-ounce custard cups. Holding cups with pot holders, quickly tilt to evenly coat bottoms of the cups.
3. Place cups in a 2-quart square baking dish. In a mixing bowl stir together eggs, pumpkin, milk, the 1/4 cup sugar, pumpkin pie spice, orange peel, and vanilla. Pour the pumpkin mixture over caramelized sugar in cups. Place the pan on the oven rack. Pour boiling water into the baking dish around cups to a depth of 1 inch.
4. Bake in a 325 degree F oven for 40 to 45 minutes or until a knife inserted near the centers comes out clean. Remove cups from water. Cool slightly on wire rack. Cover and chill for 4 to 24 hours.
5. To serve, loosen edges of flans with a knife, slipping the point of the knife down the sides to let in air. Invert a dessert plate over each flan; turn custard cup and plate over together. Scrape the caramelized sugar that remains in cup onto the flan. If desired, garnish with pomegranate seeds.