A new approach to the efficient basis set for accurate molecular calculations: Applications to diatomic molecules

The method of the bond function basis set combined with the counterpoise procedure is studied in detail by the complete fourth‐order Mo/ller–Plesset perturbation (MP4) theory, following from a recent communication report [J. Chem. Phys. 98, 2481 (1993)]. This method is applied to calculate molecular dissociation energies De as well as equilibrium bond distances re and harmonic frequencies ωe of a number of diatomic molecules (N2, O2, F2, Cl2, HF, HCl, and CO) and the results are compared with those from other methods, without either counterpoise procedure or bond functions or both. The usefulness of the method is shown by the results for all the molecules using a moderately polarized basis set (2p1d for H atom and 2d1f for heavy atoms) augmented with the universal bond functions 3s3p2d. The method has consistently recovered 98%–99% of the experimental values for De, compared to as low as 90% without bond functions. The effect of bond functions is less significant on the predictions of re and ωe, due prima...

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