The propagation of basis set error and geometry optimization in ab initio calculations. A statistical analysis of the sulfur d‐orbital problem
作者： Paul G. Mezey , Ernst ‐C. Haas
DOI: 10.1063/1.443903
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摘要: By generating a sample of 100 random molecular basis sets from normal distribution centered on the best‐energy, fully variational AO sets, statistical analysis has been carried out distributions and pair correlations calculated Hartree–Fock total energies, optimum bond lengths, energy components, formal atomic charges. Dimethylsulfoxide (DMSO), geometry which found extremely sensitive to variations in an earlier study, selected as model compound. The results provide clear answer sulfur d‐orbital problem, since no simultaneous reproduction experimental adequate approximation variationally have possible without including d‐polarization functions sulfur.
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