Just upgraded to CS6 targeting the mSATA. On start there was an immediate error "Could not open a scratch file because the file is locked." Apparently, there is a bug in CS6 where it insists on using the C: drive, where I no longer have a Users directory. Looking across the net I found some clues.
After a bit of experimenting, one did work. I held down just CTRL-ALT then went to the Start menu to start Photoshop CS6. A menu appears to specify the Scratch Disk and I point it to D:. The picture above was edited using Photoshop, so it worked!