For hydrogen molecular ion, it is shown that the James function is an approximation to the more general Guillemin and Zener wavefunction. From IsO" and 2pO", Guillemin and Zener orbitals, a correlated wavefunction of H2 is constructed. It contains all the terms which occur in the James and Coolidge wavefunction for H. molecule. The proposed function for H2 is dealt with in parts so as to study the contributions from configuration interaction and the correlation factor to the total binding energy of the H2 molecule.
The semiempirical diatomics-in-molecules theory is used to predict potential-energy surfaces for the ground and several excited electronic states of the system H4. Results are presented for linear (D∞h), rectangular (D2h), square (D4h), “perpendicular” (D2d), tetrahedral (Td), and rhombic (D2h) conformations. Results are compared with those from previous ab initio calculations. The lowest energy state of square H4 is singlet; the optimum internuclear distance is R = 2.0 bohrs, for which the energy is 67.8 kcal/mole higher than 2E(H2) (fixed nuclei energies). Vibrational frequencies for this square are computed: 2180, 1210, 1990, 1470, 1470, and 2280i cm−1, the latter corresponding to the reaction coordinate for the H2, H2 bimolecular exchange reaction. The specific rate constant for this reaction is computed according to the absolute rate theory.
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