Although diazirines have been used as precursors for carbene generation for more than thirty years, little is known about the reaction mechanisms. Modern theory predicts that the characteristic absorption of ground state diazirine and of dimethyldiazirine above 300 nm is due to an n to π* transition. In the gas-phase the n π* excited state deactivates by passage through a conical intersection to form a diradical like structure. Theory has not yet considered the photophysics of asymmetrically substituted diazirines, in either the gas phase, polar, or non-polar solvents. We will present our first attempt in elucidating the photochemistry and photophysics of arylhalodiazirines and suggested zwitterions as intermediates in the photochemical formation of arylhalocarbenes.