Chemical Shift of Solvated Hydride Ion: Comparative Study with Solvated Fluoride Ion

Imamura, Kosuke; Higashi, Masahiro; Kobayashi, Yoji; Kageyama, Hiroshi; Sato, Hirofumi

doi:10.1021/acs.jpcb.2c00326

Cited by 4 publications

(4 citation statements)

References 41 publications

(83 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…31 P NMR chemical shifts in Pd complexes were computed using DFT theory by Latypov et al 159 BOPHY-fullerene C60 dyad was studied by Heredia et al 160 as a photosensitizer for antimicrobial photodynamic therapy. Chemical shift of solvated hydride ion and fluorine ion was studied by Sato et al 161 Experimental studies of small molecules in the gas phase are used as reference for benchmark calculations of NMR parameters. Such studies are important for providing absolute nuclear magnetic shieldings and magnetic moments of small molecules diluted in an inert gas.…”

Section: Nuclear Shielding Calculation In Natural Productsmentioning

confidence: 99%

Theory and computation of nuclear shielding

2023

Nuclear Magnetic Resonance

View full text Add to dashboard Cite

This chapter continues earlier reviews of essential works on theoretical issues of nuclear magnetic shieldings published from 1 January to 31 December 2022. As previously, the chapter concentrates on theoretical calculations of nuclear shielding parameters and/or chemical shifts in case of free molecules in the gas phase and solution, and in some cases in the solid state using a periodic formulation. The nuclear shieldings in solution are mainly calculated using inexpensive polarizable continuum model of solvent (PCM). The use of discrete solvent molecules (in particular water and other polar solvents), which is essential for correct description of hydrogen bonding, is often omitted by numerous authors. Most calculations use a relatively simple and fast, but reliable density functional theory (DFT) combined with gauge-including atomic orbital (GIAO) approach. On the other hand, reports on prediction of nuclear magnetic shielding parameters using high level theoretical methods combined with large and flexible basis sets are not so common due to the enormous computational cost. In addition, correction of raw theoretical nuclear magnetic shieldings due to ro-vibration (zero-point vibration correction, ZPVC) and temperature corrections (TC), as well as implicit and explicit solvent effects and relativistic corrections are not often reported.

show abstract

Section: Nuclear Shielding Calculation In Natural Productsmentioning

confidence: 99%

Theory and computation of nuclear shielding

2023

Nuclear Magnetic Resonance

View full text Add to dashboard Cite

show abstract

“…In its pyramidal structure like that of the H 3 O + cation, 3 the [H 3 O] − anion is a hypothetical double Rydberg anion. 4 However, the most stable conformation of [H 3 O] − is a hydride H − bound to a water H 2 O molecule, with the hydride acting as a strong base, 5 which is likely to deprotonate the water molecule. In this regard, the properties of the [H 3 O] − anion are an intimate part of the prototypical anion−molecule reaction…”

Section: ■ Introductionmentioning

confidence: 99%

“…In its pyramidal structure like that of the H 3 O + cation, the [H 3 O] − anion is a hypothetical double Rydberg anion . However, the most stable conformation of [H 3 O] − is a hydride H – bound to a water H 2 O molecule, with the hydride acting as a strong base, which is likely to deprotonate the water molecule. In this regard, the properties of the [H 3 O] − anion are an intimate part of the prototypical anion–molecule reaction normalH − + normalH 2 normalO ↔ false[ normalH 3 normalO false] − ↔ OH − + normalH 2 + 0.367 .25em eV first reported as early as 1957 by Muschlitz, and has intrigued theoreticians and experimentalists ever since.…”

Section: Introductionmentioning

confidence: 99%

Zero-Point-Energy Driven Isotopic Exchange of the [H₃O]⁻ anion Probed by Mid-Infrared Action Spectroscopy

Dinu,

Ončák,

Thorwirth

et al. 2024

J. Am. Chem. Soc.

View full text Add to dashboard Cite

We present the first observation of vibrational transitions in the [H 3 O] − anion, an intermediate in the anion−molecule reaction of water, H 2 O, and hydride, H − , using a laser-induced isotopic H/D exchange reaction action spectroscopy scheme applied to anions. The observed bands are assigned as the fundamental and first overtone of the H 2 O−H − vibrational stretching mode, based on anharmonic calculations within the vibrational perturbation theory and vibrational configuration interaction. Although the D 2 O•D − species has the lowest energy, our experiments confirm the D 2 O•H − isotope to be a sink of the H/D exchange reaction. Ab initio calculations corroborate that the formation of D 2 O•H − is favored, as the zero-pointenergy difference is larger between D 2 and H 2 than between D

show abstract

“…As the Zn(Cd)F2 concentration increases, the peak gradually shifts upfield, indicating that the 19 F nucleus is shielded. Water molecules make F − less shielded [15], resulting in a downfield shift. Therefore, the shielding effect of 19 F nucleus in current solutions comes from the interference of cations.…”

Section: Introductionmentioning

confidence: 99%

Structural hysteresis of dilute fluorine salt aqueous solutions

Zhang,

Wang,

Luo

et al. 2023

Preprint

View full text Add to dashboard Cite

In contrast with the generally accepted picture for most of the dilute salt aqueous solutions, which defaults that only one structural state/form exists at the given values of system/thermodynamic parameters, in this work, combining characterization of 19F nuclear magnetic resonance, ultraviolet-visible spectroscopies with theoretical calculations, we found that the F−-bearing aqueous solutions with identical component, but prepared by both different pathways, one of which is by mixing subsaturated MF2 solutions and Na//ClO4−(SO42−) solutions (path 1) and another is by mixing concentrated M2+//ClO4−(SO42−) solutions (M = Zn, Cd, Co and Cu) and NaF solution (path 2), can long-termly exist spectrographic distinguishable different thermodynamic steady states, in which the F− in the former preferentially exists in the form of more M2+-F− contact ion pairs (CIP), whereas in the form of more, even all M2+-F− solvent-separated/shared ion pairs (SIP) for the latter. This results from the different solution initial states, where path 1 solutions contain certain amounts of CIPs, whereas there is no CIPs initially in path 2 solutions, the high energy barrier of conversion between SIP and CIP, coupling with the low concentration gradient and thereby small conversion driving force. This makes the solutions exhibit an unusual “apparent” structural hysteresis. Due to the universality of the causes, present findings can expand to other sparingly soluble salts and enhance the significance of solution preparation bias on the thermodynamic studies in solution chemistry domain of sparingly soluble salts.

show abstract

Chemical Shift of Solvated Hydride Ion: Comparative Study with Solvated Fluoride Ion

Cited by 4 publications

References 41 publications

Theory and computation of nuclear shielding

Theory and computation of nuclear shielding

Zero-Point-Energy Driven Isotopic Exchange of the [H₃O]⁻ anion Probed by Mid-Infrared Action Spectroscopy

Structural hysteresis of dilute fluorine salt aqueous solutions

Contact Info

Product

Resources

About

Chemical Shift of Solvated Hydride Ion: Comparative Study with Solvated Fluoride Ion

Cited by 4 publications

References 41 publications

Theory and computation of nuclear shielding

Theory and computation of nuclear shielding

Zero-Point-Energy Driven Isotopic Exchange of the [H3O]− anion Probed by Mid-Infrared Action Spectroscopy

Structural hysteresis of dilute fluorine salt aqueous solutions

Contact Info

Product

Resources

About

Zero-Point-Energy Driven Isotopic Exchange of the [H₃O]⁻ anion Probed by Mid-Infrared Action Spectroscopy