Get Color Indices
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get_color_indices in combination with get_color_tuple will retrieve the RGB values for colors.
print cmd.get_color_indices()
will retrieve the Pymol color names and corresponding internal color indices.
print cmd.get_color_tuple(index-number)
will retrieve individual RGB components when index-number is replaced with one of the color indices from above.
The color index, an integer, gets returned when color is returned while Iterate. You can thus use the get_color_tuple command above to convert that to RGB color values if you need to use the colors outside Pymol.
set_color color-name, [r,b,g]
will create a new color that will appear in the GUI list. From the open-source GUI you can use the "add" button in the color list viewer. In MacPyMOL, enter the new name into the MacPyMOL color editor window, set the RGBs, and then click Apply.