Spa. Sauer et al., THE VIBRATIONAL AND TEMPERATURE-DEPENDENCE OF THE MAGNETIC-PROPERTIESOF THE OXONIUM ION (H3O+), Chemical physics, 184(1-3), 1994, pp. 1-11
First- and second-order polarization propagator calculations of magnet
izability, rotational g-factor, spin-rotation constant, and hydrogen a
nd oxygen shielding property surfaces are reported for the gas phase o
xonium ion. Using these surfaces and the nonrigid inverter ro-vibratio
nal eigenfunctions, effective magnetic molecular constants are obtaine
d for the lowest ro-inversional states of (H3O+)-O-17 and (D3O+)-O-17.
The predicted constants exhibit sizable and non-monotonic dependence
on the vibrational and rotational quantum numbers. We find nearly temp
erature independence of both the H-1 and O-17 shieldings, mainly due t
o cancellation effects between contributions from the inversional and
the symmetric stretching modes. We compute a downfield shift in H-1 as
well as O-17 Shieldings of H3O+ relative to pure water in agreement w
ith earlier observations. The influence of hydrogen bonding on these s
hifts, as well as on the deuterium-induced isotope shifts on the O-17
shielding, is discussed.