Analysis of the D and 17O Quadrupole Coupling Constants in Ice Ih

Abstract

Hydrogen bondformation in enriched heavy ice is observed experimentally to alter the D and 17O quadrupole coupling constants relative to the vapor. In this study the dependence of these coupling constant shifts on electronic structure is examined theoretically with two types of all‐electron, single‐determinant wavefunctions constructed from Slater‐orbital basis sets for the water monomer, dimer, trimer, and pentamer. SCF computations are first performed with the various multimers constrained to a geometry based on the observed structure of ice (Ih). The sensitivity of these results to geometry and to the electron distribution is then examined with bond‐orbital wavefunctions. It is concluded that the solid—vapor coupling‐constant shifts can be accounted for with a representation of the crystal which includes exchange forces between bonds, direct charge transfer due to hydrogen bondformation, and elongation of the normal O – D bond. The relative importance of these contributions is discussed for both nuclei.