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We know from after images that violet-yellow, blue-orange and green-magenta are perceptual complementaries.

When I am designing I would like a hue wheel that reflects these perceptual complementaries. So yellow would be at 90° (instead of 60°) opposite violet at 270°. And when a field of orange at 50% opacity is layered over blue the product would be grey.

Is this possible? I have tried changing colour modes in photoshop but the Hue slider/wheel always seems to be the same. Do I need to change the working space? If so what do I need to change it to?

Just to be clear this isn't a question about the differences between rgb and cmyk. I would like to have a hue wheel that represents the perceptual complementaries and for blend modes to work based on perceptual complenetaries.

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I believe what you are seeking is not a working space but a completely separate color model.

Color models have set values and thus set compliments. The RGB, CMYK, and LAB color models can't be changed.

Color spaces alter saturation, vibrance, and value of the given color model hues. Color spaces do not alter default hues. Default hues are controlled by the Color Model.

You would need an entirely new color model not simply a color space.

Now, this is not to say a "perceptual RGB color model" does not exist. It may. I've simply never seen such an animal.

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An excellent answer that clarifies a frequent misconception. I would only add the fact that, in the parlance of color management, use of the word "perceptual" is nearly always in reference to the perceptual rendering intent -- one of the four rendering intents described in the ICC spec: en.wikipedia.org/wiki/Color_management#Rendering_intent – fish2000 Aug 22 '12 at 8:02

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