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Four things:
1) Choose good location and background, pre-scouted ideally
2) Choose the right lighting kit, experiment, test beforehand or at least game it out in your head
3) Watch out for little things before finally firing the shutter, like a tie out of place or too many stray strands of hair
4) Make chit chat with the model while you're setting up and as you're about to take the shot, to such a degree that they become a little unfocused and less aware that the camera is there- then shoot