Second derivatives of nuclear shielding constants with respect to an electric field, i.e., shielding polarizabilities, have been calculated for the noble gas atoms from helium to xenon. The calculations have been carried out using the four-component relativistic Hartree-Fock method. In order to assess the importance of the individual relativistic corrections, the shielding polarizabilities have also been calculated at the nonrelativistic Hartree-Fock level, with spinorbit and scalar ~Darwin and mass-velocity! effects having been established by perturbative methods. Electron correlation effects have been estimated using the second-order polarization propagator approach. The relativistic effects on the tensor components of the shielding polarizabilities are found to be larger and changing less regularly with the atomic number than for the shielding constant itself. However, there is a partial cancellation of the contributions to the parallel and perpendicular components of the shielding polarizability and as a consequence the mean shielding polarizability is far less affected than the individual components.
Electric field effects on the shielding constants of noble gases: a 4-component relativistic Hartree-Fock study
Rizzo A
2004
Abstract
Second derivatives of nuclear shielding constants with respect to an electric field, i.e., shielding polarizabilities, have been calculated for the noble gas atoms from helium to xenon. The calculations have been carried out using the four-component relativistic Hartree-Fock method. In order to assess the importance of the individual relativistic corrections, the shielding polarizabilities have also been calculated at the nonrelativistic Hartree-Fock level, with spinorbit and scalar ~Darwin and mass-velocity! effects having been established by perturbative methods. Electron correlation effects have been estimated using the second-order polarization propagator approach. The relativistic effects on the tensor components of the shielding polarizabilities are found to be larger and changing less regularly with the atomic number than for the shielding constant itself. However, there is a partial cancellation of the contributions to the parallel and perpendicular components of the shielding polarizability and as a consequence the mean shielding polarizability is far less affected than the individual components.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
