Hyperfine coupling of the hydrogen atom in high temperature water

Nuzhdin, Kirill B.; Bartels, David M.

doi:10.1063/1.4795005

Cited by 3 publications

(7 citation statements)

References 49 publications

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“…This behavior was rationalized with a clathrate model wherein vibrational motions of the hydrogen atom leading to collisions with the clathrate wall allow delocalization of its spin onto neighboring water molecules, with a smaller contribution from compression of the wave function due to its confinement in the cage. A very recent work extends the study to still higher temperatures, finding that A / A vac reaches a minimum of 0.9918 at 513 K and then rises with further increase in temperature to 0.9923 at 573 K . The latter data was found to fit a quadratic behavior with temperature, which was rationalized by adding to the wall collision and compression mechanisms another effect from the wall collision frequency, where changes with temperature of the water density and the hydrogen atom partial molar volume alter the mean free path, along with a simple ansatz for the effectiveness of each collision.…”

Section: Introductionmentioning

confidence: 63%

“…Experimental measurements of the hydrogen atom hyperfine coupling constant , have been interpreted with a model that envisions the H* to be vibrating inside a spherical cage with a characteristic frequency arising from a radial harmonic potential. However, examination of the Fourier transforms of our mean square displacements does not show any evidence of a particular vibrational frequency.…”

Section: Transportmentioning

confidence: 99%

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Hydrogen Atom in Water from Ambient to High Temperatures

Pomogaeva

Chipman

2013

J. Phys. Chem. B

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The aqueous hydrogen atom is studied with molecular dynamics simulations from ambient temperature to near the critical point. The radial distribution functions find a hydrogen atom coordination number of about 13 water molecules at 300 K to about 4 water molecules at 646 K. The radial and angular distribution functions indicate that first-shell water molecules tend to orient to maximize hydrogen bonding interactions with other water molecules. These orientational tendencies diminish with temperature. The calculated diffusion coefficient agrees very well with experimental results known near ambient temperatures. It fits a simple activation model to about 575 K, above which the diffusion becomes much faster than predicted by the fit. To temperatures of at least 500 K there is evidence for caging on a time scale of about 1 ps, but the evidence disappears at very high temperatures. Values of the aqueous hydrogen hyperfine coupling constant are obtained by averaging the results of density functional calculations on clusters extracted from the simulations. The hyperfine coupling calculations do not agree well with experiment for reasons that are not understood now, pointing to the need for further research on this problem.

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Section: Introductionmentioning

confidence: 63%

Section: Transportmentioning

confidence: 99%

Hydrogen Atom in Water from Ambient to High Temperatures

Pomogaeva

Chipman

2013

J. Phys. Chem. B

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“…52 These values are significantly shifted by an average of -1900 ppm from the free electron g factor of 2.0023 (using the Gaussian definition g = g free + ppm/10 6 ). Fessenden and Verma 50 demonstrated a small trend toward larger (more negative) shift at higher temperature.…”

Section: Resultsmentioning

confidence: 99%

A Simple ab Initio Model for the Hydrated Electron That Matches Experiment

et al. 2015

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Since its discovery over 50 years ago, the “structure” and properties of the hydrated electron has been a subject for wonderment and also fierce debate. In the present work we seriously explore a minimal model for the aqueous electron, consisting of a small water anion cluster embedded in a polarized continuum, using several levels of ab initio calculation and basis set. The minimum energy zero “Kelvin” structure found for any 4-water (or larger) anion cluster, at any post-Hartree-Fock theory level, is very similar to a recently reported embedded-DFT-in-classical-water-MD simulation (UMJ: Uhlig, Marsalek, and Jungwirth, Journal of Physical Chemistry Letters 2012, 3, 3071-5), with four OH bonds oriented toward the maximum charge density in a small central “void”. The minimum calculation with just four water molecules does a remarkably good job of reproducing the resonance Raman properties, the radius of gyration derived from the optical spectrum, the vertical detachment energy, and the hydration free energy. For the first time we also successfully calculate the EPR g-factor and (low temperature ice) hyperfine couplings. The simple tetrahedral anion cluster model conforms very well to experiment, suggesting it does in fact represent the dominant structural motif of the hydrated electron.

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“…However, by working in analogy with the pKa of HClO2, we suggest that the pKa of HBrO2 is (3.16 ± 0.10) at µ = 1.0 M. This leads to E°' = (1. 30 [5], which 3636 adjusts the derived I2 •-/2Ipotential to +1.05 V.…”

Section: Discussion 3561 3562mentioning

confidence: 99%

“…For the hydrogen atom, the radii from 15 data sets in the literature were averaged to yield a value of (114 ± 6) pm in this recent review [28]. Other, non-crystallographic values not included are (100 ± 10) pm from an extrapolation to zero dipole moment in hydrogen halides [29] and 92 pm from an analysis of the hyperfine coupling by EPR spectroscopy [30].…”

Section: Rare Gas Solubilitymentioning

confidence: 99%

Standard electrode potentials involving radicals in aqueous solution: inorganic radicals (IUPAC Technical Report)

2016

Chemistry International

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The fourth IUPAC/IUPAP Joint Working Party (JWP) on the priority of claims to the discovery of new elements 113, 115, 117 and 118 has reviewed the relevant literature pertaining to several claims. In accordance with the Criteria for the discovery of elements previously established by the 1991 IUPAC/IUPAP Transfermium Working Group (TWG), and reinforced in subsequent IUPAC/IUPAP JWP discussions, it was determined that the RIKEN collaboration has fulfilled those Criteria for element Z = 113. The Dubna-Livermore-Oak Ridge collaborations claims for 115 and 117 are also in compliance. The discussion of element Z = 118 will appear in a subsequent report. A synopsis of experiments and related efforts is presented along with some commentary guiding future applications of the Criteria. The fourth IUPAC/IUPAP Joint Working Party (JWP) on the priority of claims to the discovery of new elements 113, 115, 117 and 118 has reviewed the relevant literature pertaining to several claims. In accordance with the criteria for the discovery of elements previously established by the 1991 IUPAC/IUPAP Transfermium Working Group (TWG), and reinforced in subsequent IUPAC/IUPAP JWP discussions, it was determined that the Dubna-Livermore collaboration has fulfilled those criteria for element Z = 118. A synopsis of experiments and related efforts is presented. Computational drug design is a rapidly changing field that plays an increasingly important role in medicinal chemistry. Since the publication of the first glossary in 1997, substantial changes have occurred in both medicinal chemistry and computational drug design. This has resulted in the use of many new terms and the consequent necessity to update the previous glossary. For this purpose a Working Party of eight experts was assembled. They produced explanatory definitions of more than 150 new and revised terms. Recommendations are made for standard potentials involving select inorganic radicals in aqueous solution at 25 °C. These recommendations are based on a critical and thorough literature review and also by performing derivations from various literature reports. The recommended data are summarized in tables of standard potentials, Gibbs energies of formation, radical pK a 's, and hemicolligation equilibrium constants. In all cases, current best estimates of the uncertainties are provided. An extensive set of Data Sheets is appended that provide original literature references, summarize the experimental results, and describe the decisions and procedures leading to each of the recommendations .

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Hyperfine coupling of the hydrogen atom in high temperature water

Cited by 3 publications

References 49 publications

Hydrogen Atom in Water from Ambient to High Temperatures

Hydrogen Atom in Water from Ambient to High Temperatures

A Simple ab Initio Model for the Hydrated Electron That Matches Experiment

Standard electrode potentials involving radicals in aqueous solution: inorganic radicals (IUPAC Technical Report)

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