Solving the electron and electron-nuclear Schrodinger equations for the excited states of helium atom with the free iterative-complement-interaction method.
Very accurate variational calculations with the free iterative-complement-interaction (ICI) method for solving the Schrodinger equation were performed for the 1sNs singlet and triplet excited states of helium atom up to N=24. This is the first extensive applications of the free ICI method to the calculations of excited states to very high levels. We performed the calculations with the fixed-nucleus Hamiltonian and moving-nucleus Hamiltonian. The latter case is the Schrodinger equation for the electron-nuclear Hamiltonian and includes the quantum effect of nuclear motion. This solution corresponds to the nonrelativistic limit and reproduced the experimental values up to five decimal figures. The small differences from the experimental values are not at all the theoretical errors but represent the physical effects that are not included in the present calculations, such as relativistic effect, quantum electrodynamic effect, and even the experimental errors. The present calculations constitute a small step toward the accurately predictive quantum chemistry.
Nakashima
Hiroyuki
H
Quantum Chemistry Research Institute, JST CREST, Kyodai Katsura Venture Plaza 106, Kyoto, Japan.
Hijikata
Yuh
Y
Nakatsuji
Hiroshi
H