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This is due to the scattering of light...
Actually during sunset/sunrise only longer wavelength reach our eyes not shorter because shorter one get scattered easily.
This is the basic reason behind seeing reddish color.
amanmishra97:
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As the distance of travel through the atmosphere increases during dawn and dusk, light is refracted much more than during noon. ... As the shorter wavelengths are scattered, only red light is left, as it has the largest wavelength of the seven colours. Thus the sun appears red during sunrise and sunset.
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