Hydrogen energy is considered as one of the ideal green energy sources due to its superior features such as high energy density and low pollution. The solar hydrogen generation via photocatalytic water splitting has attracted tremendous attention since it has great potential for low-cost and clean hydrogen production. Recently, the water dissociation on TiO2 has been intensively studied and plenty of impressive works have been done. However, for the surface reaction mechanism of this process, there still remain some bottlenecks to solve. In this research we apply first principal calculations using density functional theory (DFT) with HSE 06 functional on the high-performance computational platform of Cluster Engine to comprehensively study the change of adsorption energy with different coverages of hydrogen on rutile TiO2 (110) surface and the localized sites of electrons. Additionally, other important information including energy band and DOS are also discussed. Therefore, the theory study can provide guidance and support for the possible future hydrogen generation application.