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> something to do with the physics of absorbing light to drive a chemical reaction

Exactly that. Blue does two steps of the process, while red does only one. There's a cost for synthesizing all that machinery, so absorbing green would just be not worth it.

> 450nm and 680nm are not harmonics

In fact they're in 3:2 ratio with 1% margin. But they don't have to be. Take a look at fluorescence: it converts one wavelength to another, and they don't have to be multiples of each other. Once photon gets absorbed onto a chemical, the electronic structure of the molecule decides what will happen to it.



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