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Variable ζ calculation for self‐consistent screening parameters in ab initio molecular theory
Author(s) -
Selsby R. G.
Publication year - 1975
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560090110
Subject(s) - adiabatic process , chemistry , molecular orbital , linear combination of atomic orbitals , ab initio , ionization energy , ion , series (stratigraphy) , ionization , electron affinity (data page) , charge (physics) , atomic physics , computational chemistry , molecular physics , physics , thermodynamics , molecule , quantum mechanics , paleontology , organic chemistry , biology
A resolution of Roothaan's HF–SCF–LCAO–MO equations is proposed in which atomic orbital exponents (ζ) are made dependent on the molecular charge distribution and included in the self‐consistent scheme. Screening parameters so obtained are self‐consistent with the molecular orbital coefficients and compare closely to optimum orbital exponents found by other methods. The technique is applied to the ground, lowest positive, and lowest negative ion states of the hydride series LiH, BH, and HF. Calculated potential curves are used to define purely theoretical values for the vertical and adiabatic ionization energies and electron affinities. Predictions are compared to experimental values where available.