The electric field gradient (EFG) at the nucleus, the generalized Sternheimer shielding constants, and the EFG hyperpolarizabilities of a set of reference molecules are computed using analytic density-functional theory (DFT) quadratic response theory. At the three-parameter Becke--parameter-Lee--Yang--Parr (B3LYP) level, DFT underestimates correlation effects compared with accurate coupled-cluster and multiconfigurational self-consistent field estimates. For the prediction of EFG properties of hydrogen nuclei and electron-rich atoms such as halides, B3LYP even provides less reliable results than Hartree--Fock theory.
Sternheimer shieldings and EFG polarizabilities: a density-functional theory study
Rizzo A;
2003
Abstract
The electric field gradient (EFG) at the nucleus, the generalized Sternheimer shielding constants, and the EFG hyperpolarizabilities of a set of reference molecules are computed using analytic density-functional theory (DFT) quadratic response theory. At the three-parameter Becke--parameter-Lee--Yang--Parr (B3LYP) level, DFT underestimates correlation effects compared with accurate coupled-cluster and multiconfigurational self-consistent field estimates. For the prediction of EFG properties of hydrogen nuclei and electron-rich atoms such as halides, B3LYP even provides less reliable results than Hartree--Fock theory.File in questo prodotto:
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