Abstract
The NMR chemical shifts of hydride andfluoride ions in the solutionphase are evaluated from thefirst principle. The cluster structure in thefirst solvationshell is calculated by density functional theory and MP2 theory, and the solvent effectaround the cluster is considered by PCM and RISM-SCF-SEDD methods. Theobtained shifts are analyzed in terms of electronic structure and solvent effects and arecompared with available experimental data. Thefluoride ion is deshielded in thepresence of solvent molecules compared to the isolated state due to a largerparamagnetic contribution from the 2p orbital. On the other hand, there is no suchchange for the hydride ion. The paramagnetic and diamagnetic contributions are slightlychanged due to the solvation, but they are canceled out. As a result, the chemical shift of the hydride ion is less affected by thesolvent than that of thefluoride ion. The increased diamagnetic contribution of hydride ion dissolved in the solvent is attributed tothe change in electron density coupled with microscopic solvation