A systematic comparison of molecular properties obtained using Hartree–Fock, a hybrid Hartree–Fock density‐functional‐theory, and coupled‐cluster methods

We present results of a systematic study of the theoretical determination of equilibrium geometries, harmonic frequencies, total atomization energies, and dipole moments using Hartree–Fock, a hybrid Hartree–Fock density‐functional‐theory, and coupled‐cluster methods in conjunction with a triple zeta basis set for a large set of molecules. This allows a direct comparison of the three theoretical methods applied to a range of chemical systems. The average errors (‖experimental value‐theoretical value‖) for the Hartree–Fock, hybrid Hartree–Fock density‐functional‐theory, and coupled‐cluster methods, respectively, are bond length (A) 0.022, 0.005, 0.005; bond angle (degrees) 2.7, 1.7, 1.9; harmonic frequencies (cm−1) 144, 40, 30; atomization energies (kcal/mol) 81.9, 3.6, 11.5; and dipole moments (debye) 0.29, 0.14, 0.10. This clearly demonstrates that the relatively inexpensive hybrid Hartree–Fock density‐functional‐theory method yields results which represent a reliable, significant improvement over those obtained with the Hartree–Fock method. The results obtained using the hybrid Hartree–Fock density‐functional‐theory method are, in fact, quite comparable with the corresponding results obtained using the high level, ab initio coupled‐cluster method. For certain difficult open shell examples, the hybrid Hartree–Fock density‐functional theory using a spin restricted open shell Hartree–Fock density is much improved over the corresponding hybrid Hartree–Fock density‐functional‐theory results obtained using a spin unrestricted Hartree–Fock density.

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