The question popped into my mind when i was looking at some slightly molten chocolate toppings on my cake, they were definitely much shinier than just the cold ones. They werent molten enough to lose their pyramid shape, they were just shinier and less viscus
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The surface is smoother. When it cools down the surface is not quite as uniform, and chocolate in particular tends to form crystals in it I think which would make it rougher.
Trickier, notice how wet things (anything, like cloth, skin, etc.) are shinier when wet but also tend to look darker. Modelling this properly is a problem in computer graphics.
Short answer: Specifically for chocolate, it’s the coco butter. The warm cocoa butter in the chips creates a smooth surface allowing light to reflect.
Longer answer: Your chips were warmed to a temperature high enough to melt the cocoa butter (about 90F/32.2C) but not high enough to make the chocolate lose the drop shape (for milk chocolate, about 104F/40C). As the chocolate cools, the surface ‘clumps’ (or crystalizes if the temper is really off) meaning the light no longer has a smooth surface to reflect off of.
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