Hydrogen Atom of KH<sub>2</sub>AsO<sub>4</sub> Determined by Neutron Diffraction Study

Miyoshi, Tatsuki; Akimoto, Tomoshi; Mashiyama, Hiroyuki

doi:10.1143/jpsj.80.074607

Cited by 4 publications

(3 citation statements)

References 15 publications

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“…This is different from ferroelectric croconic acid, where we observed strongly asymmetric C–O–H···OC hydrogen bonds, much more asymmetric than in other C–O–H···OC hydrogen bonds of comparable length . On the other hand in KH 2 PO 4 -type ferroelectrics and in antiferroelectric squaric acid the hydrogen nucleus is in an O–H···O hydrogen bond well displaced from the hydrogen bond donor toward the center of the hydrogen bond, what makes the bond less asymmetric. The reason for this difference is not known.…”

Section: Discussioncontrasting

confidence: 86%

Nuclear Quadrupole Resonance Study of Hydrogen Bonds in Solid 2-Methylbenzimidazole and 5,6-Dimethylbenzimidazole

Seliger

Žagar

2013

J. Phys. Chem. C

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Substituted imidazole and benzimidazole often form polar hydrogen-bonded chains in the solid state. 2-Methylbenzimidazole is known to be a high-temperature organic ferroelectric. We have measured temperature dependences of 14 N nuclear quadrupole resonance (NQR) frequencies and proton T 1 in 2-methylbenzimidazole and 5,6-dimethylbenzimidazole. The NQR frequencies are assigned to amino and imino nitrogen positions. The NQR data exclude the possibility of proton two-site exchange in an N−H•••N hydrogen bond. The activation energies for the methyl group hindered rotation are determined in both compounds. The present 14 N NQR data are compared to the published 14 N NQR data in solid substituted and coordinated imidazoles, in substituted benzimidazoles and in imidazole in the gas phase. A linear correlation between the two inplane principal values of the quadrupole coupling tensor and the out-ofplane principal value of the quadrupole coupling tensor is observed in imidazole, ranging from the amino nitrogen position to the imino nitrogen position. Transition from the amino to the imino nitrogen position is determined on the correlation diagram. The correlation diagram can be used to quantitatively observe the asymmetry of the N−H•••N hydrogen bond. A similar correlation diagram is proposed also for substituted benzimidazoles. The magnitudes of the principal values of the 14 N quadrupole coupling tensor in ferroelectric 2-methylbenzimidazole show that the macroscopic ferroelectric ordering has in this compound a minor effect on the asymmetry of the N−H•••N hydrogen bonds.

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Section: Discussioncontrasting

confidence: 86%

Nuclear Quadrupole Resonance Study of Hydrogen Bonds in Solid 2-Methylbenzimidazole and 5,6-Dimethylbenzimidazole

Seliger

Žagar

2013

J. Phys. Chem. C

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“…In case of the two-site exchange, in the high-temperature phase, we expect deuteron to be close to the center of the hydrogen bond and not close to the oxygen atom. Also, the neutron diffraction studies of DPDA give a single deuteron position in the high temperature phase and not two position as for example observed in KH 2 AsO4 …”

Section: Discussionmentioning

confidence: 89%

“…Also, the neutron diffraction studies of DPDA 2 give a single deuteron position in the high temperature phase and not two position as for example observed in KH 2 AsO4. 33 The 14 N NQR results and the hydrogen bond parameters are summarized in Table 1.…”

Section: ■ Discussionmentioning

confidence: 99%

Nuclear Quadrupole Resonance Study of Proton and Deuteron Migration in Short Strong Hydrogen Bonds Formed in Molecular Complex 3,5-Dinitrobenzoic Acid–Nicotinic Acid and in Deuterated 3,5-Pyridinedicarboxylic Acid

et al. 2016

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Temperature dependences of the 14 N nuclear quadrupole resonance (NQR) frequencies have been measured in molecular complex 3,5-dinitrobenzoic acid−nicotinic acid (35DBNA) and in deuterated 3,5-pyridinedicarboxylic acid (DPDA). In deuterated DPDA, the temperature dependences of the deuterium quadrupole coupling constants and asymmetry parameters η have also been measured. In 35DBNA, the magnitude of the quadrupole coupling constant of the pyridine nitrogen agrees with the experimentally observed proton transfer. No proton exchange (O−H···N ↔ O − ···H−N + ) is observed. The temperature dependence of the 14 N quadrupole coupling constant is analyzed in a model of a resonance hybrid of two extreme electron configurations of the molecules. The energy difference of the two extreme electron configurations is determined. In the same model, we analyzed previously published 14 N NQR data of the NHO hydrogen bond in nondeuterated 3,5-pyridinedicarboxylic acid. The 14 N NQR data in DPDA show the presence of a quasi-continuous isosymmetric phase transition at around 210 K. No mixture of the high-temperature phase and the low-temperature phase has been observed below this temperature. We analyzed the temperature dependence of the 14 N quadrupole coupling constant in DPDA in the model of a resonance hybrid of two extreme electron configurations and determined the temperature dependences of their contributions to the electronic state of the molecule. ■ INTRODUCTIONHydrogen bonding is an important chemical interaction that occurs in a variety of organic and inorganic materials. These bonds, which are largely electrostatic in nature, are weaker than covalent and ionic bonds but stronger than ordinary dipole− dipole and dispersion forces. Hydrogen bonding plays a crucial role in many biological processes. It is further connected to some interesting physical properties including ferroelectricity, pyroelectricity, nonlinear optical properties, among others.Short strong hydrogen bonds (SSHB) possess a strongly covalent character. An interesting phenomena occurring in SSHB is temperature-dependent proton migration that has been observed by inelastic neutron scattering in 3,5-pyridinedicarboxylic acid (PDA), 1,2 urea phosphoric acid, 3,4 a 1:2 cocrystal of benzene-1,2,4,5-tetracarboxylic acid and 4,4-bipyridyl, 5 a 1:1 crystal of 2-methylpyridine and pentachlorophenol, 6 pyridinium 2,4-dinitrobenzoate, 7 3,5-dinitrobenzoic acid−3,5-dimethylpyridine complex, 8 dimethylurea−oxalic acid complex, 9 and in molecular complex 3,5-dinitrobenzoic acid− nicotinic acid (35DBNA). 10 The variable-temperature X-ray and neutron diffraction study of 35DBNA indicates a significant degree of proton transfer in the short NHO hydrogen bond. Complementary ab initio MD simulations at 400 K show the key proton hopping across the NHO short strong hydrogen bond, spending short periods along the trajectory (8% of the simulation time) bonded to the O atom. 10 Deuteration of a strong hydrogen bond is known to strongly change its properties. 11 Well-known effects a...

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Theoretical investigation, of Cochran’s mode frequency, and electrical permittivity of KH2AsO4 (KDA) crystal by using Zuberav’s statistical Green function technique

Kumar¹,

Upadhyay²

2022

Materials Today: Proceedings

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Hydrogen Atom of KH₂AsO₄ Determined by Neutron Diffraction Study

Cited by 4 publications

References 15 publications

Nuclear Quadrupole Resonance Study of Hydrogen Bonds in Solid 2-Methylbenzimidazole and 5,6-Dimethylbenzimidazole

Nuclear Quadrupole Resonance Study of Hydrogen Bonds in Solid 2-Methylbenzimidazole and 5,6-Dimethylbenzimidazole

Nuclear Quadrupole Resonance Study of Proton and Deuteron Migration in Short Strong Hydrogen Bonds Formed in Molecular Complex 3,5-Dinitrobenzoic Acid–Nicotinic Acid and in Deuterated 3,5-Pyridinedicarboxylic Acid

Theoretical investigation, of Cochran’s mode frequency, and electrical permittivity of KH2AsO4 (KDA) crystal by using Zuberav’s statistical Green function technique

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Hydrogen Atom of KH2AsO4 Determined by Neutron Diffraction Study

Cited by 4 publications

References 15 publications

Nuclear Quadrupole Resonance Study of Hydrogen Bonds in Solid 2-Methylbenzimidazole and 5,6-Dimethylbenzimidazole

Nuclear Quadrupole Resonance Study of Hydrogen Bonds in Solid 2-Methylbenzimidazole and 5,6-Dimethylbenzimidazole

Nuclear Quadrupole Resonance Study of Proton and Deuteron Migration in Short Strong Hydrogen Bonds Formed in Molecular Complex 3,5-Dinitrobenzoic Acid–Nicotinic Acid and in Deuterated 3,5-Pyridinedicarboxylic Acid

Theoretical investigation, of Cochran’s mode frequency, and electrical permittivity of KH2AsO4 (KDA) crystal by using Zuberav’s statistical Green function technique

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Hydrogen Atom of KH₂AsO₄ Determined by Neutron Diffraction Study