We report the first ever accurate theoretical prediction of thermal conductance of any material interface. Thermal interfacial conductance of aluminum (Al)-sapphire ({\alpha}-Al2O3) interface along crystal directions (111) Al || (0001) Al2O3 for temperature ranging from 50-500 K is calculated using two fundamentally different methods: interfacial conductance modal analysis (ICMA) and atomistic green function (AGF). While AGF overpredicts interfacial conductance, both the quantitative and qualitative predictions of ICMA are exceptional when compared with the time-domain thermoreflectance (TDTR) experimental data. The mean error in ICMA results are below 5%. We believe that the accurate theoretical prediction by ICMA can be credited to a more fundamental treatment of the interfacial heat flux in contrast to that of the phonon gas model (PGM) and inclusion of anharmonicity to full order. ICMA also gives the eigen mode level details revealing the nanoscale picture of heat transport: more than 90% of conductance is contributed by the cross correlation (interaction) between partially extended modes of Al and Al2O3 and the remaining is attributed to interfacial modes. This is a major milestone in combustion heat transfer research enabling materials scientists to rationally design propellant architectures to serve long-distance propulsion missions.