Line an 8 x 8-inch pan with nonstick foil or spray foil with cooking spray; set aside.
In a small saucepan, combine the water, sugar, and 3 tablespoons light corn syrup, stirring gently to bring the sugar into the liquid without letting it stick to the pan sides.
Clip in a candy thermometer and heat over medium-high until the syrup reaches the soft-ball stage (about 235°F / 118°C), stirring occasionally to dissolve sugar.
Remove from heat, stir in the 3 tablespoons melted butter, then immediately pour the hot syrup over the Rice Krispies and stir quickly until the cereal is evenly coated.
Press the coated cereal firmly and evenly into the prepared pan using a silicone spatula; let the crust cool to room temperature.
For the peanut butter–chocolate layer, place the peanut butter and 1/2 cup chocolate in a large microwave-safe bowl and heat in short bursts, stirring until melted and smooth.
Spread the peanut butter–chocolate mixture evenly over the cooled cereal crust and chill for about 1 hour to set.
For the dark chocolate icing, heat 1/2 cup dark chocolate, 1 tablespoon corn syrup, and 1 tablespoon butter in a microwave-safe bowl in short bursts, stirring until smooth.
Pour the melted dark chocolate icing over the peanut butter layer and spread evenly, then chill until the top is firm, about 1 hour.
Remove the bars from the pan using the foil, cut into 9 squares, and store in the refrigerator.