Computational schemes are presented with which to evaluate the electrostatic Coulomb energy in relativistic molecular electronic structure calculations using a basis of four-component Dirac spinor amplitudes. We demonstrate that algorithms may be constructed and implemented which differ only in minor details from those in common use in nonrelativistic quantum chemistry, and that the four-component formalism is neither as complicated nor as expensive as has been suggested recently in the literature. Spherically symmetrical atomic basis sets are presented which indicate that accurate representations of the Coulomb energy may be obtained using modest expansions of the electronic density in a scalar auxiliary basis set of spherical harmonic Gaussian-type functions.
Evaluation of the Coulomb energy in relativistic self-consistent field theory
BELANZONI, Paola;SGAMELLOTTI, Antonio
2002
Abstract
Computational schemes are presented with which to evaluate the electrostatic Coulomb energy in relativistic molecular electronic structure calculations using a basis of four-component Dirac spinor amplitudes. We demonstrate that algorithms may be constructed and implemented which differ only in minor details from those in common use in nonrelativistic quantum chemistry, and that the four-component formalism is neither as complicated nor as expensive as has been suggested recently in the literature. Spherically symmetrical atomic basis sets are presented which indicate that accurate representations of the Coulomb energy may be obtained using modest expansions of the electronic density in a scalar auxiliary basis set of spherical harmonic Gaussian-type functions.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
