The bottom graph shows an overlay of the yellow you get from mixing pure red and green light and what you would get from a light source of the right frequency for yellow. As you can probably see it's off not just by a scaling factor vertically, but the second half of the wave is closer than the first half. This phenomenon would persist with different colors even if a yellow led was added and after that an orange, etc.Though it would improve with each addition. Maybe one day they'll make an led that can actually be any different color from the spectrum by altering the voltage source to it, so they don't have to add different colors of light to try and make all the colors.
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