Strange that you want to increase heat transfer from a hot tank, but whatever. Tanks store fluids. To change the properties (temperature, pressure, etc.) other devices should be used. Changing temperature is best done with a heat exchanger, not a tank. You can modify the tank to make it more like a heat exchanger (add penetrations and cross- or counter-flow, add fins and other means of increasing surface area, etc.), or pipe a closed recycle loop through a heat exchanger, or ...
But rounding the corners would seem to lower, not increase, the heat-exchanger-iness of the tank, like SandCounter said.