Coherent anti-Stokes Raman spectroscopy has been used to study deuterium at ambient temperature to 187 GPa, the highest pressure this technique has ever been applied. The pressure dependence of the nu1 vibron line shape indicates that deuterium has a rho direct=0.501 and rho exciton=0.434 mol/cm3 for a band gap of 2omega P=4.66 eV. The extrapolation from the ambient pressure band gap yields a metallization pressure of 460 GPa, confirming earlier measurements. Above 143 GPa, the Raman shift data provide clear evidence for the presence of the ab initio predicted I' phase of deuterium.