Journal of Computer Chemistry, Japan -International Edition
Online ISSN : 2189-048X
ISSN-L : 2189-048X
Relativistic DFT Calculations of Changes in NMR Chemical Shifts in Aqueous Solutions of Heavy-Metal Nitrates
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2022 Volume 8 Article ID: 2021-0048


The NMR chemical shifts for metal ions in aqueous solutions of inorganic salts often change with the solution concentration. These changes are referred to herein as dilution–concentration (dc) shifts. For main-group elements, the dc shifts generally increase with increasing atomic number. We calculated the dc shifts for various metal and nonmetal ions in aqueous nitrate solutions of elements in periods 5 and 6 by the DFT method based on the spin–orbit ZORA Hamiltonian. The calculation results revealed that the dc shifts of metal and nonmetal ions with the outermost shell electron configuration of 6s2 are primarily determined by the changes in the spin–orbit interaction terms of the shielding constants. Furthermore, the spin densities of the Pb(II) ions in aqueous lead nitrate solutions under an external magnetic field were calculated using the matrix/modified Dirac–Kohn–Sham Hamiltonian, which confirmed the presence of Fermi contacts between the spin-polarized electrons and the lead nucleus. When a suitable threshold for visualizing the spin density was set, there was no Fermi contact in the infinite dilution state, whereas the upward-spin electron was in Fermi contact with the lead nucleus in the saturation state. There have been few reports of the NMR chemical shifts of heavy atoms in terms of Fermi contacts with relativistically spin-polarized electrons. We succeeded in clarifying how the dc shifts occur on the hydrated ions of heavy atoms by visualizing the Fermi contact of spin-polarized electrons with heavy-metal nuclei.

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