DeeDee,
I agree with Chris that early light and late afternoon light are lovely to shoot in. Of course, it all depends on your objective: if you're trying to get real moody lighting, then early dawn can provide some gorgeous colors and mist which diffuses the light and produces some really nice effects.

I like to shoot at sunset and put that behind the subject and use my 580 flash for primary illumination being careful to expose so that the sunset colors are properly exposed.

On the other hand, if you're going to shoot to create a painting or where detail is very important, any time of day is great as long as you and the subject are in open shade to reduce the shadows.

Sounds like a lovely shoot. I'm jealous

Jim