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To begin understanding Geant4's implementation of optical physics, take a look at the following example: $G4INSTALL/examples/extended/optical/LXe
"src/LXePhysicsList.cc" and include/LXEPhysicsList.hh show how to implement optical physics
"src/LXeDetectorConstruction.cc" (lines 145-165) show how to define a scintillating material as well as geometry
"src/LXeSteppingAction.cc" shows in great detail how to "detect" optical photons at a photoconversion surface (photomultiplier tube in this case) as well as extract detailed information about optical processes of photons at an optical boundary.
You can use LXe as an example that you modify to suit your needs. You will need to fully understand the optical properties of your scintillating materials and optical readout devices (almost all available on manufacturer's websites) in order to implement your problem.
You should also carefully read Chapter 5.2.5 ("Optical processes") in the Geant4 User's Guide: http://geant4.web.cern.ch/geant4/UserDocumentation/UsersGuides/ForApplicationDeveloper/html/ch05s02.html#sect.PhysProc.Photo
Hope that helps.