We present laser-driven shock compression experiments on cryogenic liquid deuterium to 550 GPa along the principal Hugoniot and reflected-shock data up to 1 TPa. High-precision interferometric Doppler velocimetry and impedance-matching analysis were used to determine the compression accurately enough to reveal a significant difference as compared to state-of-the-art ab initio calculations and thus, no single equation of state model fully matches the principal Hugoniot of deuterium over the observed pressure range. In the molecular-to-atomic transition pressure range, models based on density functional theory calculations predict the maximum compression accurately. However, beyond 250 GPa along the principal Hugoniot, first-principles models exhibit a stiffer response than the experimental data. Similarly, above 500 GPa the reflected shock data show 5%-7% higher compression than predicted by all current models.