Hydrogen Bond Symmetrization in Glycinium Oxalate under Pressure

Bhatt, Himal; Murli, Chitra; Mishra, Ajay K.; Verma, Ashok; Garg, Nandini; Deo, M. N.; Читра, Р.; Sharma, Surinder M.

doi:10.1021/acs.jpcb.5b11507

Cited by 44 publications

(37 citation statements)

References 93 publications

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“…Our high pressure IR and Raman studies have shown a dynamic sharing of the proton between the two semioxalate units of glycinium oxalate, thus mimicking a symmetric hydrogen bond state. These results were corroborated with the help of ab initio calculations which showed that the probability of crossing the midpoint between the oxalates increased with pressure 127 .…”

Section: Organic Molecular Solidssupporting

confidence: 58%

High Pressure:One of the many Tools to Study Material Properties at Extreme Conditions

Garg¹

2017

Current Science

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High pressure is a powerful and clean variable, which when applied can bring about large changes in structure and properties of materials. It can be used to simulate the conditions found deep inside the earth or in different planetary interiors. It is widely used in chemical industry, especially when the chemical reaction products have lower volumes than the initial reactants, and also in the food preservation industry, where it ensures that aromas and flavours are not lost even after preservation. Materials under pressure can be studied both theoretically and experimentally. In this article apart from discussing how to set up a basic high pressure experiment using the DAC, some examples have been elaborated to show how both experiments and theory complement each other and both put together can help in a deeper understanding of the changes brought about by application of high pressure.

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Section: Organic Molecular Solidssupporting

confidence: 58%

High Pressure:One of the many Tools to Study Material Properties at Extreme Conditions

Garg¹

2017

Current Science

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“…For example, under compression of the O:H-O bond, the H-O covalent bond becomes longer while the total O–O distance is shortened, leading to the proton centring in the O–O of ice VIII-X phase transition21011121314. The behaviour of the proton is so strange that thermal fluctuation15 and quantum effect of nuclei16 were both considered contributing to the ambiguous behaviour.…”

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confidence: 99%

Hydrogen-bond potential for ice VIII-X phase transition

Zhang

Chen

2016

Sci Rep

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Repulsive force between the O-H bonding electrons and the O:H nonbonding pair within hydrogen bond (O-H:O) is an often overlooked interaction which dictates the extraordinary recoverability and sensitivity of water and ice. Here, we present a potential model for this hidden force opposing ice compression of ice VIII-X phase transition based on the density functional theory (DFT) and neutron scattering observations. We consider the H-O bond covalent force, the O:H nonbond dispersion force, and the hidden force to approach equilibrium under compression. Due to the charge polarization within the O:H-O bond, the curvatures of the H-O bond and the O:H nonbond potentials show opposite sign before transition, resulting in the asymmetric relaxation of H-O and O:H (O:H contraction and H-O elongation) and the H+ proton centralization towards phase X. When cross the VIII-X phase boundary, both H-O and O:H contract slightly. The potential model reproduces the VIII-X phase transition as observed in experiment. Development of the potential model may provide a choice for further calculations of water anomalies.

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“…The crystal structure of BA is built of two parallel sets of dimers and supported by two 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 Thus, the symmetrization of hydrogen bond is expected in BA at higher pressures, which can be found in many compounds containing X-H···X hydrogen bonds. 5,15,[21][22][23] Moreover, the difference of bond length between C-O and C=O as a function of pressure is shown in Figure S5. One can see that the difference of bond length between C-O and C=O is continuous decreasing when pressure is increasing, which indicate the symmetrization of hydrogen bonds will eliminate the distinction between single and double C-O bonds.…”

Section: Resultsmentioning

confidence: 99%

“…A number of investigations on the structural behaviors of hydrogen-bonded molecular crystals under high pressure have been reported. [11][12][13][14][15][16][17][18][19][20] For example, urea experienced four structural changes at 0.48, 0.6, 2.8, and 7.2 GPa, respectively. [17][18] During the phase transitions, large variations were observed in hydrogen bonds, including breakage, formation, and distortion.…”

Section: Introductionmentioning

confidence: 99%

“…20 Besides, pressure-induced hydrogen bond symmetrization is also of significant importance, which helps to understand proton dynamics in the complex biological processes in nature. 5,15,[21][22][23] Overall, pressure is a powerful tool for investigating hydrogen-bonded molecular crystals, which is of fundamental importance not only for scientific research but also for potential practical applications.…”

Section: Introductionmentioning

confidence: 99%

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High Pressure Structural Investigation of Benzoic Acid: Raman Spectroscopy and X-ray Diffraction

Kang

Wang

et al. 2016

J. Phys. Chem. C

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The structural stability of benzoic acid (C 6 H 5 COOH, BA), a hydrogen-bonded molecular crystal, has been investigated by Raman spectroscopy and angle-dispersive X-ray diffraction (ADXRD) up to ~ 18 GPa at room temperature. Under ambient conditions, benzoic acid molecules are arranged in two set of parallel planes and held together by hydrogen bonding and van der Waals interactions. Small changes (e.g., emergence of new peaks, splitting of original peaks) can be observed in the Raman spectra at high pressures. However, no obvious changes can be observed in the X-ray diffraction measurements, which rules out any symmetry/structure changes within this pressure range. The pressure dependence of lattice parameters are presented, which show monotonously decrease without any anomalies. The experimental isothermal pressure-volume data are well fitted by the third-order Birch-Murnaghan equation of state, yielding bulk modulus 0 B = 41.7(6) GPa and a first pressure derivative ' 0 B = 4.5(4). Axial compressibility shows obvious anisotropy, the a-axis is more compressible than b-axis and c-axis. Moreover, the near symmetrization limit of hydrogen bonds at high pressures is proposed from the first-principles calculations.Based on the Raman, XRD, and the first-principles calculations analysis, we propose that the high pressure structural stability of benzoic acid is associated with the special hydrogen-bonded dimer structure.

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Hydrogen Bond Symmetrization in Glycinium Oxalate under Pressure

Cited by 44 publications

References 93 publications

High Pressure:One of the many Tools to Study Material Properties at Extreme Conditions

High Pressure:One of the many Tools to Study Material Properties at Extreme Conditions

Hydrogen-bond potential for ice VIII-X phase transition

High Pressure Structural Investigation of Benzoic Acid: Raman Spectroscopy and X-ray Diffraction

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