Nuclear moments and electron density matrices in atoms

An electron density matrix approach for the determination of nuclear multipole moments is presented. The electronic matrix elements entering the expressions of the experimentally observed hyperfine coupling constants of atoms are expressed as functionals of the electron charge or spin density matrices. In principle, the calculation of these functionals could be made using any (relativistic or not) molecular orbital (MO) or DFT method. The electronic matrix elements for all possible hyperfine interaction operators, including the yet unobserved magnetic octupole couplings, are considered. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2004