Rayleigh Scattering describes how light hits the atmosphere and scatters inelastically, bouncing off itself and other molecules. Light with the shortest wavelengths, blue, collides with the molecules of the atmosphere more because of its rapid oscillation and therefore is scattered the most. The rest of the light falls to Earth, but we see the scattered blue light.
Similarly, when the sun is setting, the light must travel through a greater amount of atmosphere to reach us because of its angle. By the time it reaches our eyes, even the low frequency wavelengths have been scattered and we see the orange and red light.
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