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Extra resources for Advances in Chemical Physics: Intermolecular Forces, Volume 12
0 (ref. 7 (ref. 2 (ref. 29b). fully minimized and hence the close agreement between the nonadiabatic and experimental dissociation energies may be fortuitous. These calculations show that the Born-Oppenheimer approximation is excellent and the deviations from it are small even for H, (at least for the ground state, see subsection 2 below). For molecules with nuclei of greater mass, the Born-Oppenheimer approximation should be even more accurate. 24 J. 0. HIRSCHFELDER AND W. J. MEATH 2. The Lowest Excited Bound State, B'C;, of Hydrogen Kolos and WolniewiczZ3have also calculated the energy of dissociation (from the bottom of the potential energy curve) for the lowest of hydrogen using a 54-term wave function.
On the other hand, at smaller separations the state corresponds to a (lsa)(2sa)configuration. A 20-term open-shell covalent-type wave function was used for the calculation at the inner minimum. These results are discussed in terms of electron correlation in Section VII. B. Large Separations One of the principal difficulties with Rayleigh-Ritz variational calculations of the interaction energy at large separations is that one cannot calculate the interaction energy directly using this method. Rather, one obtains the interaction energy, Eq.
This quadrupole-type resonance should be much weaker than the dipole but, nevertheless, it should be recognized and expected in S-D, P-F, etc. collisions between like atoms. d. The Second-Order Energy. The second-order energy for resonant interactions of two like atoms has the same form as for nonresonant interactions (since the cross terms vanish because of selection rules). However, the induction energy is given by 42 J. 0. HIRSCHFELDER AND W. J. MEATH and the dispersion energy is given by e.