Ab initio
"Ab initio" quantum mechanical and chemical methods may be used to calculate the potential energy of a system on the fly, as needed for conformations in a trajectory. This calculation is usually made in the close neighborhood of the reaction coordinate. Although various approximations may be used, these are based on theoretical considerations, not on empirical fitting. "Ab initio" calculations produce a vast amount of information that is not available from empirical methods, such as density of electronic states or other electronic properties. A significant advantage of using "ab initio" methods is the ability to study reactions that involve breaking or formation of covalent bonds, which correspond to multiple electronic states. Moreover, "ab initio" methods also allow recovering effects beyond the Born–Oppenheimer approximation using approaches like mixed quantum-classical dynamics.