If you use optical mice, then USB will usually be smoother than PS/2.
However, the opposite is true for ball mice (because you can set the ps2 poll rate to 200 hz, whereas USB's poll rate is locked at 125).
I'm using a Logitech MouseMan Wheel (5 years old, ball mouse, ps2) and I prefer its movement over all optical mice that I've used (which includes the Logitech MouseMan Optical, Microsoft's Intellimouse Optical, and the Kensington Optical)