Photoshop is heavily multithreaded, so quad > dual. At least if you're looking at benchmarks that simulate heavy use and emphasize the things where Photoshop is CPU limited.
Photoshop isn't as heavily multithreaded as some things, but there'll still be a benefit. Although frankly, depending on his usage patterns, he may not notice much of a difference, and he may be I/O (HD) limited if he doesn't have an SSD.
Also, if he's doing web design, he might have to occasionally transcode some video. Then he'll be glad he has a quad core.
But as a general rule anyway, get the quad. Quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad quad.