Potential Energy Surface Molecular Structure, Transition States, and Reaction Paths

Potential Energy Surface Molecular Structure, Transition States, and Reaction Paths 

In order to effectively solve the nuclear problem, an explicit form for the nuclear coordinates R should be provided, by defining a reference frame of axes. Such a frame is chosen in order to describe the translational, vibrational, and rotational motions of the molecule, and the Sayvez conditions are employed to decouple the three contributions in the kinetic energy. The nuclear Hamiltonian can be then written in the form [59, 60] 

Stationary points are crucial for an analysis of reaction paths and spectroscopic properties and can be found performing geometry optimizations for which several automatic algorithms are well established nowadays [63, 64]. The global (the 

Closely related to the PES is the concept of property surfaces (PSs). Molecular properties such as the dipole moment, polarizability, and NMR shielding depend on the response ofthe wave function to applied electric and/or magnetic fields and their values as functions ofthe nuclear coordinates define the various PSs. Both the potential energy and the PSs are strongly related to spectroscopic properties, 

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