The best way to do this would be to select the iris of the eyes, either with the elliptical marquee tool, the magnetic lasso tool, or the magic wand tool, and put them on their own layer by pressing Ctrl + J. (I have a description of this method in a previous tutorial) and then click back on your original photo layer and press Ctrl + Shift + U to desaturate the color from the image. If you want to exaggerate the eye color, go to Image/Adjustments/Hue/Saturation and click the Colorize option - then drag the Saturation slider to the right to intensify the color content. To change the color all together, just move the Hue slider.
Oddly enough, I have another tutorial in the works using these very same steps for something totally different!
I find that using the brush tool set at "color" or "soft light" on a new layer is a good way for me to colorize a greyscale image. I use a new layer for each different color. That way if I mess up or change my mind about a color, I only have to change one layer at a time.
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Oddly enough, I have another tutorial in the works using these very same steps for something totally different!
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