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It's a spectroscopic effect. We can easily measure the energy of light given it's frequency. E=hv.

Radiation like light can excite (electronically or vibrationally) air molecules and various other molecules in the car. Excited states of molecules are extremely short lived, thus the molecules will rapidly decay down to there ground state lg>

Upon relaxation there are several types of radiative and non-radiative decay. Since most of the matter in your car does is not fluorescent or phosphorescent the dominant decay factor in heat. Upon relaxation the molecules radiate heat, which will continue to build up in your car unless you open the windows, in which case thermodynamics tells us that the heat will flow from hot to cold.

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Q: Why interior of car parked in sun is hotter than atmosphere?
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