THE VIBRATIONAL AND TEMPERATURE-DEPENDENCE OF THE MAGNETIC-PROPERTIESOF THE OXONIUM ION (H3O+)

Citation
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
Citations number
40
Categorie Soggetti
Physics, Atomic, Molecular & Chemical
Journal title
ISSN journal
03010104
Volume
184
Issue
1-3
Year of publication
1994
Pages
1 - 11
Database
ISI
SICI code
0301-0104(1994)184:1-3<1:TVATOT>2.0.ZU;2-E
Abstract
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.