Perturbation theories for the calculation of molecular interaction energies. II. Application to H2

The many perturbation expansions reviewed in Paper I [D. M. Chipman, J. D. Bowman, and J. O. Hirschfelder, J. Chem. Phys. 59, 0000 (1973)] are applied to the interaction of a ground state hydrogen atom with a proton to form the 1s σg and 2p σu electronic states of H2+. The calculations were made with high precision for the range of separations R = 0.2–15ao using a large basis set of Slater‐type orbitals. For the polarization and symmetrized polarization methods the energies were obtained analytically, these results providing a check on the completeness of the basis set. Also, long range and short range asymptotic formulas are given for the first order wavefunctions and the perturbation energies. The HS and MSMA methods gave the best second order energies. The EL‐HAV second order energy is good at intermediate separations but becomes bad at large separations. The expectation value of the Hamiltonian using the wavefunction truncated after the first order (where the coefficient of the zero order function is ...

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