caa a22 4500 378862820 CHVBK 20180305123350.0 cr unu---uuuuu 161128e20031201xx s 000 0 eng 10.1524/zpch.217.12.1549.20471 doi (NATIONALLICENCE)gruyter-10.1524/zpch.217.12.1549.20471 Interpretation of Hydrogen/Deuterium Isotope Effects on NMR Chemical Shifts of [FHF]− Ion Based on Calculations of Nuclear Magnetic Shielding Tensor Surface [Elektronische Daten] [Nicolai S. Golubev, Sona M. Melikova, Dimitri Shchepkin, Ilja G. Shenderovich, Peter M. Tolstoy, Gleb S. Denisov] Using ab initio calculations of 1H, 19F magnetic shielding tensors of hydrogen difluoride ion as the functions of three coordinates of symmetry, an attempt is made to estimate the contributions of different vibrational isotope effects to H/D NMR isotope shifts referred in the literature. It is shown that the contributions of the amplitudes of proton stretching and bending vibrations dominate whereas the contribution of the totally symmetric vibration can be neglected. Different signs of the H/D isotope effects on hydron and fluorine chemical shifts are caused by very strong angle dependence of the fluorine magnetic shielding. The agreement of the calculated and measured values is nearly quantitative. An unusually strong paramagnetic deshielding of hydrogen for the equilibrium geometry of the [FHF]− ion is noted. © 2003 Oldenbourg Wissenschaftsverlag GmbH Thermodynamics & statistical physics nationallicence Laboratory techniques, experiments nationallicence Physical chemistry nationallicence Golubev Nicolai S. aut Melikova Sona M. aut Shchepkin Dimitri aut Shenderovich Ilja G. aut Tolstoy Peter M. aut Denisov Gleb S. aut Zeitschrift für Physikalische Chemie/International journal of research in physical chemistry and chemical physics Oldenbourg Wissenschaftsverlag GmbH 217/12/2003(2003-12-01), 1549-1564 0044-3336 217:12/2003<1549 2003 217 zpch https://doi.org/10.1524/zpch.217.12.1549.20471 text/html Onlinezugriff via DOI 1 research article jats NATIONALLICENCE 856 40 https://doi.org/10.1524/zpch.217.12.1549.20471 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Golubev Nicolai S. aut NATIONALLICENCE 700 1- Melikova Sona M. aut NATIONALLICENCE 700 1- Shchepkin Dimitri aut NATIONALLICENCE 700 1- Shenderovich Ilja G. aut NATIONALLICENCE 700 1- Tolstoy Peter M. aut NATIONALLICENCE 700 1- Denisov Gleb S. aut NATIONALLICENCE 773 0- Zeitschrift für Physikalische Chemie/International journal of research in physical chemistry and chemical physics Oldenbourg Wissenschaftsverlag GmbH 217/12/2003(2003-12-01), 1549-1564 0044-3336 217:12/2003<1549 2003 217 zpch CC0 http://creativecommons.org/publicdomain/zero/1.0 nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-gruyter