NMR chemical shifts of ice and liquid water: The effects of condensation

Journal Article · Wed Jan 12 04:00:00 EST 2000 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/ja991961k· OSTI ID:20017342

Pfrommer, B G; Mauri, F; Louie, S G

The authors report the results of ab initio density functional theory calculations of the NMR chemical shift of liquid water and hexagonal ice. Depending on the structural model used, the calculated isotropic shift of ice Ih with respect to the gas phase is {minus}8.0 {+-} 0.2 or {minus}8.1 {+-} 0.1 ppm for the proton, and {minus}48.6 {+-} or {minus}48.1 {+-} 0.02 ppm for oxygen. The proton anisotropy is {minus}33.4 {+-} 0.2 or {minus}33.6 {+-} 0.2 ppm. Using snapshots from ab initio molecular dynamics simulation, a gas-to-liquid shift of {minus}5.8 {+-} 0.1 ppm for hydrogen, and {minus}36.6 {+-} 0.5 ppm for oxygen were found. Molecules beyond the firs solvation shell influence the proton chemical shift predominantly via the electric field generated by their permanent electric dipole moment. Finally, it was shown that it is possible to reproduce the proton chemical shifts in the condensed phases by an empirical function of the local molecular geometry.

• Research Organization: Univ. of California, Berkeley, CA (US)
• Sponsoring Organization: National Science Foundation; US Department of Energy
• DOE Contract Number: AC03-76SF00098
• OSTI ID: 20017342
• Journal Information: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 1 Vol. 122; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ANISOTROPY
CHEMICAL SHIFT
ICE
NUCLEAR MAGNETIC RESONANCE
STRUCTURAL MODELS
VAPOR CONDENSATION
WATER