Electronic Structure of Diatomic Molecules. VI.A. Hartree—Fock Wavefunctions and Energy Quantities for the Ground States of the First-Row Hydrides, AH

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Hartree—Fock wavefunctions are presented for the LiH(X1Σ+), BeH(X2Σ+), BH(X1Σ+), CH(X2Πr), NH(X3Σ−), OH(X2Πi), and HF(X1Σ+) molecules. These are the analytic self-consistent-field wavefunctions obtained from the solutions of the Hartree—Fock—Roothaan equations. Large sets of Slater-type functions centered on both nuclei were used as the expansion basis, and extensive optimization of the orbital exponents has been carried out. The total energies obtained for Re(exptl) are −7.98731, −15.15312, −25.13137, −38.27935, −54.97806, −75.42083, and −100.07030 hartrees, respectively, for the AH hydrides listed above. The first ionization potentials, which are obtained from the Hartree—Fock energy differences between AH and AH+ systems, are 7.02, 8.14, 8.45, 10.08, 12.82, 11.44, and 14.54 eV, respectively. In addition, potential curves, spectroscopic constants, and certain other energetic quantities are presented. Crude estimates of the correlation energy of the first-row hydrides are made and such quantities are compared within the series and with their respective united and separated atoms. These results suggest that the changes in correlation energy of AH relative to the correct united atom is independent of which hydride is involved and the change is small.