The answer is [Rayleigh scattering](https://en.wikipedia.org/wiki/Rayleigh_scattering) .
In brief, the molecules in our atmosphere tend to scatter light at the blue end of the light spectrum *more readily* than red light.
That means with the sun high overhead, we see lots of that blue scattered light — it’s hitting our eyes from all directions in the sky.
Around sunset, with the sun low on the horizon, we’re seeing sunlight that’s had to aim “sideways” through a much longer geometrical length of the atmosphere before it reaches us. By the time it gets to us, much of the blue light has been already scattered & left behind. Leaving mainly the reddish end of the light spectrum to illuminate clouds & scatter in the sky at sunset.
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