Systematic computational study of the geometrical dependence of deuterium quadrupole interaction parameters in an O–2H⋯OC hydrogen bonded system Original Research Article

A systematic theoretical study of the geometrical dependence of deuterium (2H) quadrupole interaction parameters (quadrupole coupling constant and asymmetry parameter) in O–2H⋯OC hydrogen bonds is reported, using the water–formaldehyde complex as a model system. From ab initio HF–SCF calculations (using 6-31G** basis set), the principal components of the electric field gradient tensor at the 2H nucleus, and hence the quadrupole interaction parameters of the 2H nucleus, have been determined as a function of the intermolecular geometry of the complex. The results provide a systematic understanding of the dependence of quadrupole interaction parameters on hydrogen bonding geometry, and may be applied in order to guide the interpretation of experimental results, for example in the case of solid state 2H-NMR of hydrogen bonded systems.