There are several methods. Here's one I'm fond of:
Duplicate the Background layer
Go to Filter>Other>High Pass. Begin with the Radius at 0, and slowly take it up and find the sweet spot where the freckles are being exaggerated the most (the whole image will be grey at this point). As you play with the slider, you'll see that if you go too low, the freckles won't be getting their maximum punch, but if you go too high, the freckles won't be getting any additional punch, all you'll be doing is exaggerating other things. Find that sweet spot.
After pressing OK to perform the High Pass filter, change the layer's blend mode to "Hard Light".
Finally, add a mask to the layer and mask it to the freckled part of the face only.
By the way, if you want an even stronger result, you can duplicate that High Pass layer. Heck, I suppose you could duplicate it as many times as you want, but it would start to look a bit weird.
Oh, also by the way, you can use "Overlay" blend mode for a slightly gentler result than Hard Light gives.
Here's my play with the above method: