1) Check out the Summer of Malmo, if you haven't already. (Use the search function, or just use Google.)
2) Some decades back, it was found that doubles produced greater fitness than singles, in a very wide variety of sports activities. (Interestingly, the same research found no additional benefit when the doublers moved to triple sessions.)
3) Though most people do the easier run in the morning, there's nothing wrong with having your "main" session in the AM--and if you're running in considerable heat, it's probably smarter to do it then.
4) For me, personally, and for many of my students, doubles made a striking difference in fitness level--even if the total mileage was not much more than for singles. However, you should be able to build to *somewhat* more miles-per-week and actually have it feel easier than when you were doing singles.
5) General advice is to start with 2-3 nonconsecutive "double days" per week, then add another day every couple of weeks. You may find that the optimum number of double days *for you* could be anywhere between three and seven per week.
6) Be sure you're getting just as much sleep as you did when running singles. Don't short your sleep (and other recovery) to get the doubles in.
Good luck. Please periodically keep us posted on your progress.