I book a large portion of my sessions about 2 hours before sunset, and its not because I want great pictures with the sunset in the background. It is because the light is so soft and beautiful when captured properly. Photographers will often refer to this time period as the "Golden Hour" and for good reason. Not only is it great for portrait photographers, but it also brings out the best in scenery for landscape photographers as well. The colors tend to be more vibrant and the earth more alive.
Sunset light also has many great qualities such as being easier on the skin, has a nice glowing quality under the right circumstances and creates beautiful portraits.
Mid-day sun is very harsh, creates hot spots and brings out imperfections in the skin (such as wrinkles and dark circles around the eyes) and clothing. Of course, mid-day photoshoots are possible and some photographers rock them, but there is less flexibility and options available.
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