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The more air that the sunlight passes through the more of the higher frequencies are absorbed. When the sun is on the horizon (sunrise or sunset) the light reaching you from the sun changes from yellow to orange, then to red as the sunlight passes through more and more air.

There is one additional phenomenon in play. The "wedge" of air between you and the sun sometimes acts as a prism and splits the light into its spectral colors. This gives rise to the rare "green flash" just at sunset.

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