TY - JOUR
T1 - Comparison of FSGO, Hartree-Fock-Roothaan and pseudopotential calculations for Li2
AU - Ratner, Mark A.
AU - Frost, Arthur A.
AU - Topiol, Sid
AU - Sabin, John R.
N1 - Funding Information:
Perhaps the most surprising result of the present work is the great sensitivity of both the subminimal basis FSGO calculation and the large-basis HFR to fine details of the pseudopotential : qualitatively, HFR and FSGO pseudopotentials are similar, but they yield different results in either valence-only calculations. This conclusion, which was already clear from the poor results yielded by many previous pseudo- potential calculations, points out once again the necessity to construct pseudo- potentials only with extreme care and caution.23 Acknowledgement is made to the National Science Foundation and to the Univer- sity of Florida for a grant of computer time.
PY - 1978
Y1 - 1978
N2 - Plots of the pseudopotentials, valence orbitals and their differences for FSGO, large-basis Hartree-Fock-Roothaan and pseudopotential calculations on Li2 are presented. In agreement with earlier arguments, it is concluded that the success of the FSGO procedure depends upon a balanced description of core and valence orbitals. If the description of the core is improved compared to the simple FSGO single-Gaussian characterization, the use of simple FSGO for the valence density is not well attuned to the (more structured) core, and poor results are obtained. Conversely, a proper FSGO pseudopotential yields highly satisfactory FSGO valence orbitals, but is not successful if applied in a large-basis ab initio calculation.
AB - Plots of the pseudopotentials, valence orbitals and their differences for FSGO, large-basis Hartree-Fock-Roothaan and pseudopotential calculations on Li2 are presented. In agreement with earlier arguments, it is concluded that the success of the FSGO procedure depends upon a balanced description of core and valence orbitals. If the description of the core is improved compared to the simple FSGO single-Gaussian characterization, the use of simple FSGO for the valence density is not well attuned to the (more structured) core, and poor results are obtained. Conversely, a proper FSGO pseudopotential yields highly satisfactory FSGO valence orbitals, but is not successful if applied in a large-basis ab initio calculation.
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U2 - 10.1039/F29787400324
DO - 10.1039/F29787400324
M3 - Article
AN - SCOPUS:37049109637
VL - 74
SP - 324
EP - 334
JO - Journal of the Chemical Society, Faraday Transactions 2: Molecular and Chemical Physics
JF - Journal of the Chemical Society, Faraday Transactions 2: Molecular and Chemical Physics
SN - 0300-9238
ER -