the color of light coming from the sun isn’t composed out of red, green and blue; it’s a continuous spectrum from red to violet, so the colors in the sunset sky are the same white light but with slightly different properties attached, parts of the light passes though clouds, parts have to reflect around the earth’s curvature, parts get red shifted by the atmosphere, etc
if you’re interested in this more you should check out how a prism refracts light and imagine both the atmosphere and the clouds as huge prisms
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