Harmony can be defined as a pleasing arrangement of parts, whether it be music, poetry, color, or even an ice cream sundae.
In visual experiences, harmony is something that is pleasing to the eye. It engages the viewer and it creates an inner sense of order, a balance in the visual experience. When something is not harmonious, it's either boring or chaotic. At one extreme is a visual experience that is so bland that the viewer is not engaged.
The human brain will reject under-stimulating information. At the other extreme is a visual experience that is so overdone, so chaotic that the viewer can't stand to look at it. The human brain rejects what it can not organize, what it can not understand. The visual task requires that we present a logical structure. Color harmony delivers visual interest and a sense of order.
In summary, extreme unity leads to under-stimulation, extreme complexity leads to over-stimulation. Harmony is a dynamic equilibrium.