Parameterized Effective Potential for Excited Electronic States

摘要

The method of the parameterized effective potential (PEP) is developed for constructing the potential curves of excited electronic states of the same symmetry. Unlike the traditional methods of the density functional theory, the PEP is constructed as the direct mapping of an external potential. The PEP generates the one-particle orbitals such that the corresponding single-determinant Kohn-Sham function constructed on their basis is orthogonal to the determinant functions of lower-lying states. A comparison of the potential curves constructed for the HeH and H_(2) molecules by the PEP method with the precision data obtained based on the time-consuming configuration interaction methods shows that the PEP method can provide good accuracy for the geometry of an equilibrium configuration and the vertical excitation energies.