Anisotropic hyperfine interactions of rare-gas nuclei near trapped hydrogen atomsa)

Morton, J. R.; Preston, K. F.; Strachb, S. J.; Adrian, Frank J.; Jette, A. Norman

doi:10.1063/1.437825

Cited by 43 publications

(19 citation statements)

References 15 publications

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“…This structure was detected in the pioneering work of Foner et al [48] and reproduced in many other studies, independent of the generation method (photolysis or radiolysis) [8,9,23,[49][50][51]. However, analysis of the structure pattern consisting of large number of anisotropic components in natural xenon was found to be quite complicated, so the trapping site nature for H atoms in solid xenon remained under discussion for a long time [49,50,53,54]. Using monoisotopic and isotopically doped xenon matrices, we have obtained conclusive evidence that more than 99% of radiolytically produced H atoms are trapped in nearly undistorted the octahedral (O h ) sites and only a very minor fraction occupies substitutional sites in the fcc xenon lattice [36].…”

Section: Production Distribution and Reactions Of Hydrogen Atomsmentioning

confidence: 77%

“…A characteristic feature of the EPR spectra of trapped H atoms in solid xenon is extended, complex superhyperfine structure (SHFS) resulting from interaction of unpaired electron with the nuclei of magnetic isotopes ( 129 Xe and 131 Xe). This structure was detected in the pioneering work of Foner et al [48] and reproduced in many other studies, independent of the generation method (photolysis or radiolysis) [8,9,23,[49][50][51]. However, analysis of the structure pattern consisting of large number of anisotropic components in natural xenon was found to be quite complicated, so the trapping site nature for H atoms in solid xenon remained under discussion for a long time [49,50,53,54].…”

Section: Production Distribution and Reactions Of Hydrogen Atomsmentioning

confidence: 98%

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The radiation-induced chemistry in solid xenon matrices

Feldman

Kobzarenko

Orlov

et al. 2012

Low Temperature Physics

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The paper presents an overview of recent studies on the radiation-chemical transformations of guest molecules in solid xenon induced by fast electrons and x-ray irradiation. Specific features of the experimental approach based on combination of matrix isolation IR and EPR spectroscopy are briefly outlined (with particular impact on using monoisotopic and isotopically enriched xenon matrices). The results reveal rich and diverse radiation-induced chemistry in solid xenon, which is considered in the following major aspects: (1) matrix-induced and matrix assisted transformations of the primary guest radical cations; (2) production and dynamics of hydrogen atoms; (3) formation of xenon hydrides. Finally, preliminary results on the radiation-induced generation of oxygen atoms and ions in solid xenon are presented.

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Section: Production Distribution and Reactions Of Hydrogen Atomsmentioning

confidence: 77%

Section: Production Distribution and Reactions Of Hydrogen Atomsmentioning

confidence: 98%

The radiation-induced chemistry in solid xenon matrices

Feldman

Kobzarenko

Orlov

et al. 2012

Low Temperature Physics

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“…Although the observation of isotropic hyperfine coupling is usually indicative of through-bond delocalization of spin density onto the nucleus of interest, through-space isotropic coupling has been observed for atoms in tight van der Waals contact, consistent with the small isotropic component observed here. 51–53 …”

Section: Resultsmentioning

confidence: 99%

Vanadyl as a Stable Structural Mimic of Reactive Ferryl Intermediates in Mononuclear Nonheme-Iron Enzymes

Martinie¹,

Pollock²,

Matthews

et al. 2017

Inorg. Chem.

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The iron(II)- and 2-(oxo)glutarate-dependent (Fe/2OG) oxygenases catalyze an array of challenging transformations via a common iron(IV)-oxo (ferryl) intermediate, which in most cases abstracts hydrogen (H•) from an aliphatic carbon of the substrate. Although it has been shown that the relative disposition of the Fe–O and C–H bonds can control the rate of H• abstraction and fate of the resultant substrate radical, there remains a paucity of structural information on the actual ferryl states, owing to their high reactivity. We demonstrate here that the stable vanadyl ion [(VIV-oxo)2+] binds along with 2OG or its decarboxylation product, succinate, in the active site of two different Fe/2OG enzymes to faithfully mimic their transient ferryl states. Both ferryl and vanadyl complexes of the Fe/2OG halogenase, SyrB2, remain stably bound to its carrier protein substrate (L-aminoacyl-S-SyrB1), whereas the corresponding complexes harboring transition metals (Fe, Mn) in lower oxidation states dissociate. In the well-studied hydroxylase, taurine:2OG dioxygenase (TauD), the disposition of the substrate C–H bond relative to the vanadyl ion defined by pulse electron paramagnetic resonance methods is consistent with the crystal structure of the reactant complex and computational models of the ferryl state. Vanadyl substitution may thus afford access to structural details of the key ferryl intermediates in this important enzyme class.

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“…A number of groups have used hydrogen halides as precursors in the investigations of the properties and reactions of these atoms. [1][2][3][4][5][6][7][8][9][10][11] One of the most important facts has been the mobilization and subsequent disappearance of hydrogen atoms at 30-40 K. 2,3,6,7,9,10 UV excitation of rare-gas matrices doped with halogen atoms leads to charge-separation and permanent trapping of positive and negative charges as shown by Fajardo and Apkarian. [12][13][14] As a consequence of charge separation and trapping, several molecular ions such as (Xe 2 H) ϩ , (Kr 2 H) ϩ , (Ar 2 H) ϩ , (I 2 H) Ϫ , (Br 2 H) Ϫ , and (Cl 2 H) Ϫ , have been observed.…”

Section: Introductionmentioning

confidence: 99%

The mechanism of formation and infrared-induced decomposition of HXeI in solid Xe

Pettersson

Nieminen

Khriachtchev

et al. 1997

The Journal of Chemical Physics

118

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Ultraviolet ͑UV͒ irradiation of HI-doped xenon matrix dissociates the precursor and leads to the formation and trapping of neutral atoms. After UV photolysis, annealing of the matrix mobilizes the hydrogen atoms at about 38 K. The mobilized hydrogen atoms react with I/Xe centers forming HXeI molecules in a diffusion controlled reaction. The formed molecules can be photolyzed with infrared ͑IR͒ irradiation at 2950-3800 cm Ϫ1 and quantitatively regenerated thermally. The formation of HXeI from neutral atoms is proved by the quantitative correlation between neutral iodine atoms and HXeI molecules in selective IR photodissociation and thermal regeneration experiments. Kinetic measurements show that the formation of HXeI from atoms is prevented by a potential barrier, which is estimated to be 700 cm Ϫ1 in magnitude. The potential barrier is proposed to originate from the avoided crossing between neutral HϩXeϩI and ionic ͑HXe͒ ϩ ϩI Ϫ singlet surfaces. The dissociation energy D 0 of HXeI with respect to the top of the potential barrier is estimated to be 2950 cm Ϫ1 and D e about 4070 cm Ϫ1 in solid Xe. The weak IR photodissociation profile of HXeI around 3000 cm Ϫ1 is measured by irradiating the sample with tunable IR source and monitoring the changes in the fundamental region. The formation mechanism from neutral atoms is believed to be valid for other similar rare-gas compounds.

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Anisotropic hyperfine interactions of rare-gas nuclei near trapped hydrogen atomsa)

Abstract: Absorption and emission spectra of Na atoms trapped in raregas matrices

Cited by 43 publications

References 15 publications

The radiation-induced chemistry in solid xenon matrices

The radiation-induced chemistry in solid xenon matrices

Vanadyl as a Stable Structural Mimic of Reactive Ferryl Intermediates in Mononuclear Nonheme-Iron Enzymes

The mechanism of formation and infrared-induced decomposition of HXeI in solid Xe

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