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Welcome to the community andyke. Hope you enjoy your stay. [excited]
Chester... he's asking HOW to do it. That image is from the movie. That's most definately 3D.
But... it should be possible with PS; at least to some extent.
I don't have time at the moment for any details... but i'll just say to start with that you'll need to separate the face into different parts/areas. Then, outline those sections. Using the Liquify or Smudge tools you can drag out the "flames". Multiple layers set to Overlay, Color Dodge, and/or Hardlight will help produce the extreme hot spots seen around the glasses, etc.
For the fire seen 'floating' out beyond his face and shoulder... a clouds filled layer with a layer mask can create that effect. Simply apply the clouds filter to the layer mask and then brush out completely the outer areas that you don't want seen.
That's all i have time to explain right now. Hopefully some others will jump on this. It would make a great challenge.
In fact... why don't you take this question over to the "Photoshop Campfire" board andyke? Post it up as a challenge. [righton]
Overlay. I did some quick fiddling and got damn fine results with Overlay.
Remember that artistic frame thing I did with Calculations > Overlay? Going to be borrowing from that.
Take your subject and extract to an alpha channel.
Take the Smudge tool and get crazy with the Cheese Whiz in the direction that you want the fire effect to go in. Top it off with some almost heavy Gauss.
Start a new Alpha channel and Clouds/Difference Clouds to taste.
Then Image > Calculation to combine the two alpha into a new one using Overlay.
Remember you extracted the subject?
Well, use that alpha to extract the subject in the layers palette, but fill the outside with 50% grey.
Cut-n-paste the funky Calculations alpha into the layer palette on top of the extracted 50% grey layer and set to Overlay.
Add an Adjustment Layer > G-Map to colourize with your favorite colours.
Then add various tweaks, like Levels or Curves or whatever. Preferably as Adjustment Layers and clip where you have to. Maybe add a touch of Guass here and there. Or maybe even try inverting various things. And don't forget that you can paint big and soft to get rid of parts that you don't like.
I went through that real quick several times with various targets, and each one was pretty good.
I wish I had time to provide some pictures, but I'm heading into some nasty time. Hopefully some of the folks around here will get the jyst of it, refine, and expound.
Okay, I didn't go far because the kids are asleep and I just couldn't resist. See attachement. This was done using the above and bare minimum tweaks.
Now, if you really want to be clever, make several alphas with Clouds/Difference Clouds and really get crazy with Calculations. Even toss in the target to do some even spiffier ChOps.
Not to mention layering it up with more blending modes. Toss in an extra layer with something a bit random and set to Exclusion or Difference or something.
I like what you've got going here Stroker. If you filled the black with dimmer flames I think it would be similar to Agent Smith.
I tried to do something with the displace filter thinking I could shape a fire cloud into something similar but the result ended up looking like fire reflected off a metallic-glassy surface. Definitely not the look I was going for. I'll keep trying and post the results when I get something more like the Agent Smith picture above.
Got yet another idea but I'm at work and can't act on it. Would a customer gradient map work as the base? Then you can paint and smudge on the layers above. Hmmmm.... (wishing there was a thinking smilie)
Agent Smith Fire Effect 
Linear Mode
