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The phenomenon is called Rayleigh scattering.

White light from the Sun is scattered going through the atmosphere. The Sun's rays coming pretty much straight down aren't scattered much, but rays going sideways through the atmosphere - the sunrise and sunset rays - are scattered. Red light is scattered least, so those sunset rays make it through to make the sky appear red, while blue rays are scattered more. The blue light rays are scattered toward the ground, and this makes the sky appear blue.

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