Chemical Shift of Solvated Hydride Ion: Comparative Study with Solvated Fluoride Ion
KAUST DepartmentPhysical Science and Engineering (PSE) Division
Embargo End Date2023-04-15
Permanent link to this recordhttp://hdl.handle.net/10754/676267
MetadataShow full item record
AbstractThe NMR chemical shifts of hydride and fluoride ions in the solution phase are evaluated from the first principle. The cluster structure in the first solvation shell is calculated by density functional theory and MP2 theory, and the solvent effect around the cluster is considered by PCM and RISM-SCF-SEDD methods. The obtained shifts are analyzed in terms of electronic structure and solvent effects and are compared with available experimental data. The fluoride ion is deshielded in the presence of solvent molecules compared to the isolated state due to a larger paramagnetic contribution from the 2p orbital. On the other hand, there is no such change for the hydride ion. The paramagnetic and diamagnetic contributions are slightly changed due to the solvation, but they are canceled out. As a result, the chemical shift of the hydride ion is less affected by the solvent than that of the fluoride ion. The increased diamagnetic contribution of hydride ion dissolved in the solvent is attributed to the change in electron density coupled with microscopic solvation.
CitationImamura, K., Higashi, M., Kobayashi, Y., Kageyama, H., & Sato, H. (2022). Chemical Shift of Solvated Hydride Ion: Comparative Study with Solvated Fluoride Ion. The Journal of Physical Chemistry B. https://doi.org/10.1021/acs.jpcb.2c00326
SponsorsK.I. thanks the Grant-in-Aid for the Japan Society for Promotion of Science (JSPS) Fellows. This work was supported by JSPS KAKENHI (Grant Nos. JP17H03009, JP20H05839, JP21J21500, and JP22H04914). Theoretical computations were partly performed using Research Center for Computational Science, Okazaki, Japan (Project: 21-IMS-C021).
PublisherAmerican Chemical Society (ACS)
- Analytical energy gradient for reference interaction site model self-consistent field explicitly including spatial electron density distribution.
- Authors: Yokogawa D, Sato H, Sakaki S
- Issue date: 2009 Dec 7
- A 3D-RISM-SCF method with dual solvent boxes for a highly polarized system: application to 1,6-anhydrosugar formation reaction of phenyl α- and β-D-glucosides under basic conditions.
- Authors: Aono S, Hosoya T, Sakaki S
- Issue date: 2013 May 7
- Solvation dynamics and energetics of intramolecular hydride transfer reactions in biomass conversion.
- Authors: Mushrif SH, Varghese JJ, Krishnamurthy CB
- Issue date: 2015 Feb 21
- Quantum chemical study of solvent and substituent effects on the 1,5-hydride shift in 2,6-dimethyl-2-heptyl cations.
- Authors: Vrcek V, Vinkovic Vrcek I, Siehl HU
- Issue date: 2006 Feb 9
- NMR spectroscopic evidence for the intermediacy of XeF(3)(-) in XeF(2)/F(-) exchange, attempted syntheses and thermochemistry of XeF(3)(-) salts, and theoretical studies of the XeF(3)(-) anion.
- Authors: Vasdev N, Moran MD, Tuononen HM, Chirakal R, Suontamo RJ, Bain AD, Schrobilgen GJ
- Issue date: 2010 Oct 4