ElectronCoupled Interaction between Nuclear Spins in HD Molecule
Abstract
Electroncoupled interaction between two nuclear spins I_{A} and I_{B} is of the form hδ_{AB}I_{A}.I_{B}. In this paper, formulas for calculating δ_{AB} are derived by using the variational method. By using these formulas, we have calculated δ_{AB} of the HD molecule at internuclear distances of 1.3, 1.4, and 1.5 atomic units. The total wave function was chosen as a linear combination of seven independent functions of ^{1}Σ_{g}^{+} symmetry, representing the unperturbed state, and several additional functions, to represent the perturbation. The average value of δ_{AB} over the zeropoint vibration, <δ_{AB}>_{00}, is found to be 37.138 cps. Further, the refinement of a part of the calculations is undertaken by use of the 11term James and Coolidge wave function. The final result is <δ_{AB}>_{00}=35.217 cps. The agreement with the observed value of 42.7+/0.7 cps is satisfactory, considering that we have used only a few terms for the additional perturbative wave function and that the result is a sum of terms which cancel each other appreciably. Contributions from each perturbing Hamiltonian and also from a set of wave functions with different symmetry character were obtained separately. The various results are presented and discussed.
 Publication:

Physical Review
 Pub Date:
 July 1958
 DOI:
 10.1103/PhysRev.111.203
 Bibcode:
 1958PhRv..111..203I