Details

Autor(en) / Beteiligte

• Hoyland, James R.
• Parr, Robert G.

Titel

Magnetic Properties of Molecules from One-Center Wavefunctions. Theory and Application to the Hydrogen Molecule

Ist Teil von

• The Journal of chemical physics, 1963-06, Vol.38 (12), p.2991-2998

Erscheinungsjahr

1963

Quelle

American Institute of Physics

Beschreibungen/Notizen

• A variational procedure is proposed for the purely theoretical calculation of the diamagnetic susceptibility and nuclear magnetic shielding constants of a molecule, given a one-center electronic wavefunction for it in the absence of a magnetic field. One performs a linear variational calculation, mixing in just those Slater determinants which the field causes to interact with the Slater determinants in the original wavefunction. A simple model is proposed, whereby one can simply estimate the magnetic properties from the original wavefunction. To illustrate the method, the susceptibility of the hydrogen molecule is computed from one simple and one more complex wavefunction expanded about the molecular center. The diamagnetic susceptibility and proton shielding constant for hydrogen then are calculated from a new single-center wavefunction expanded about one of the protons. The detailed behavior of the computed paramagnetic contribution to the magnetic properties is discussed and the results indicate that these terms are well accounted for by the proposed method. The calculated values for the susceptibility and proton shielding constant are —4.05×10—6 emu (—4.03×10—6 emu experimental) and 2.67×10—5 (2.66×10—5 experimental), respectively. Various other properties of hydrogen as calculated from the proton-center wavefunction are also given.