Phase transition and chemical reactivity of 1H-tetrazole under high pressure up to 100 GPa

Gao, D.*; Tang, X.*; Wang, X.*; Yang, X.*; Zhang, P.*; Che, G.*; Han, J.*; Hattori, Takanori; Wang, Y.*; Dong, X.*; et al.

Physical Chemistry Chemical Physics, 23(35), p.19503 - 19510, 2021/09

https://doi.org/10.1039/D1CP02913D

Pressure-induced phase transition and polymerization of nitrogen-rich molecules are widely focused due to its extreme importance for the development of green high energy density materials. Here, we present a study of the phase transition and chemical reaction of 1H-tetrazole up to 100 GPa by using Raman, IR, X-ray diffraction, neutron diffraction techniques and theoretical calculation. A phase transition above 2.6 GPa was identified and the high-pressure structure was determined with one molecule in a unit cell. The 1H-tetrazole polymerizes reversibly below 100 GPa, probably through a carbon-nitrogen bonding instead of nitrogen-nitrogen bonding. Our studies updated the structure model of the high pressure phase of 1H-tetrazole, and presented the possible intermolecular bonding route for the first time, which gives new insights to understand the phase transition and chemical reaction of nitrogen-rich compounds, and benefit for designing new high energy density materials.

Radiation-induced effects on the extraction properties of hexa--octylnitrilo-triacetamide (HONTA) complexes of americium and europium

Toigawa, Tomohiro; Peterman, D. R.*; Meeker, D. S.*; Grimes, T. S.*; Zalupski, P. R.*; Mezyk, S. P.*; Cook, A. R.*; Yamashita, Shinichi*; Kumagai, Yuta; Matsumura, Tatsuro; et al.

Physical Chemistry Chemical Physics, 23(2), p.1343 - 1351, 2021/01

https://doi.org/10.1039/D0CP05720G

The candidate An(III)/Ln(III) separation ligand hexa--octylnitrilo-triacetamide (HONTA) was irradiated under envisioned SELECT (Solvent Extraction from Liquid waste using Extractants of CHON-type for Transmutation) process conditions using a solvent test loop in conjunction with cobalt-60 gamma irradiation. We demonstrate that HONTA undergoes exponential decay with increasing gamma dose to produce a range of degradation products which have been identified and quantified by HPLC-ESI-MS/MS techniques. The combination of HONTA destruction and degradation product ingrowth, particularly dioctylamine, negatively impacts the extraction and back-extraction of both americium and europium ions. The loss of HONTA was attributed to its reaction with the solvent (-dodecane) radical cation of (HONTA + R) = (7.61 0.82) 10 M s obtained by pulse radiolysis techniques. However, when this ligand is bound to either americium or europium ions, the observed -dodecane radical cation kinetics increase by over an order of magnitude. This large reactivity increase to additional reaction pathways occurring upon metal-ion binding. Lastly nanosecond time-resolved measurements showed that both direct and indirect HONTA radiolysis yielded the short-lived (100 ns) HONTA radical cation as well as a longer-lived (s) HONTA triplet excited state. These HONTA species are important precursors to the suite of HONTA degradation products observed.

Mechanism of phase transfer of uranyl ions; A Vibrational sum frequency generation spectroscopy study on solvent extraction in nuclear reprocessing

Kusaka, Ryoji; Watanabe, Masayuki

Physical Chemistry Chemical Physics, 20(47), p.29588 - 29590, 2018/12

https://doi.org/10.1039/C8CP04558E

Mechanistic understanding of solvent extraction of uranyl ions (UO) by tributyl phosphate (TBP) will help improve the technology for the treatment and disposal of spent nuclear fuels. So far, it has been believed that uranyl ions in the aqueous phase are adsorbed to a TBP-enriched organic/aqueous interface, form complexes with TBP at the interface, and are extracted into the organic phase. Here we show that uranyl-TBP complex formation does not take place at the interface using vibrational sum frequency generation (VSFG) spectroscopy and propose an alternative extraction mechanism that uranyl nitrate, UO(NO), passes through the interface and forms the uranyl-TBP complex, UO(NO)(TBP), in the organic phase.

Pressure-induced stacking disorder in boehmite

Ishii, Yusuke*; Komatsu, Kazuki*; Nakano, Satoshi*; Machida, Shinichi*; Hattori, Takanori; Sano, Asami; Kagi, Hiroyuki*

Physical Chemistry Chemical Physics, 20(24), p.16650 - 16656, 2018/06

https://doi.org/10.1039/C8CP02565G

The structure of an aluminum layered hydroxide, boehmite (-AlOOH), as a function of pressure was studied by using synchrotron X-ray and neutron diffraction. Peak broadening and subsequent splitting, which are only found for hkl (h 0) peaks in the X-ray diffraction patterns above 25 GPa, are explained by stacking disorder accompanied with a continuously increasing displacement of the AlO octahedral layer along a-axis. This finding could be the first experimental result for the pressure-induced stacking disorder driven by the continuous layer displacement. The magnitude of the layer displacement was estimated from the X-ray scattering profile calculation based on the stacking disordered structure model. Hydrogen bond geometries of boehmite, obtained by structure refinements on the observed neutron diffraction patterns for deuterated sample up to 10 GPa, show linearly approaching O-D covalent and DO hydrogen bond distances and they could merge below 26 GPa. The pressure-induced stacking disorder would make the electrostatic potential of hydrogen bonds asymmetric, yielding less chance for the proton-tunnelling.

A Significant role of non-thermal equilibrated electrons in the formation of deleterious complex DNA damage

Kai, Takeshi; Yokoya, Akinari*; Ukai, Masatoshi*; Fujii, Kentaro*; Toigawa, Tomohiro; Watanabe, Ritsuko*

Physical Chemistry Chemical Physics, 20(4), p.2838 - 2844, 2018/01

https://doi.org/10.1039/C7CP06903K

It is thought that complex DNA damage which induces in radiation biological effects is formed at radiation track end. Thus, the earliest stage of water radiolysis at the electron track end was studied to predict DNA damage. These results indicate that DNA damage sites comprising multiple nucleobase lesions with a single strand breaks can therefore be formed by multiple collisions of the electrons within three base pairs (3bp) of a DNA strand. This multiple damage site cannot be processed by base excision repair enzymes. However, pre-hydrated electrons can also be produced resulting in an additional base lesion more than 3bp away from the multi-damage site. This clustered damage site may be finally converted into a double strand break (DSB) when base excision enzymes process the additional base lesions. These DSBs include another base lesion(s) at their termini that escape from the base excision process and which may result in biological effects such as mutation in surviving cells.

Transmutation effects on long-term Cs retention in phyllosilicate minerals from first principles

Sassi, M.*; Okumura, Masahiko; Machida, Masahiko; Rosso, K. M.*

Physical Chemistry Chemical Physics, 19(39), p.27007 - 27014, 2017/10

https://doi.org/10.1039/C7CP04496H

no abstracts in English

The Effect of dynamical fluctuations of hydration structures on the absorption spectra of oxyluciferin anions in an aqueous solution

Hiyama, Miyabi*; Shiga, Motoyuki; Koga, Nobuaki*; Sugino, Osamu*; Akiyama, Hidefumi*; Noguchi, Yoshifumi*

Physical Chemistry Chemical Physics, 19(15), p.10028 - 10035, 2017/04

https://doi.org/10.1039/C7CP01067B

In this study, the effect of hydration on the absorption spectra of oxyluciferin anion isomers in an aqueous solution is investigated for elucidating the influence of characteristic hydration structures. Using a canonical ensemble of hydration structures obtained from first-principles molecular dynamics simulations, the instantaneous absorption spectra of keto-, enol-, and enolate-type aqueous oxyluciferin anions at room temperature are computed from a collection of QM/MM calculations using an explicit solvent. It is demonstrated that the calculations reproduce experimental results concerning spectral shifts and broadening, for which traditional methods based on quantum chemistry and the Franck-Condon approximation fail because of the molecular vibrations of oxyluciferin anions and dynamical fluctuations of their hydration structures.

Structure determination of the rutile-TiO(110)-(12) surface using total-reflection high-energy positron diffraction (TRHEPD)

Mochizuki, Izumi*; Ariga, Hiroko*; Fukaya, Yuki; Wada, Ken*; Maekawa, Masaki; Kawasuso, Atsuo; Shidara, Tetsuo*; Asakura, Kiyotaka*; Hyodo, Toshio*

Physical Chemistry Chemical Physics, 18(10), p.7085 - 7092, 2016/03

https://doi.org/10.1039/C5CP07892J

no abstracts in English

The Effects of alloying and segregation for the reactivity and diffusion of oxygen on CuAu(111)

Oka, Kohei*; Tsuda, Yasutaka*; Makino, Takamasa*; Okada, Michio*; Hashinokuchi, Michihiro*; Yoshigoe, Akitaka; Teraoka, Yuden; Kasai, Hideaki*

Physical Chemistry Chemical Physics, 16(36), p.19702 - 19711, 2014/08

https://doi.org/10.1039/C4CP02675F

Temperature dependence of the Fricke dosimeter and spur expansion time in the low-LET high-temperature radiolysis of water up to 350C; A Monte-Carlo simulation study

Sanguanmith, S.*; Muroya, Yusa*; Tippayamontri, T.*; Meesungnoen, J.*; Lin, M.; Katsumura, Yosuke*; Jay-Gerin, J.-P.*

Physical Chemistry Chemical Physics, 13(22), p.10690 - 10698, 2011/06

https://doi.org/10.1039/c1cp20293f

Monte-Carlo simulations of the radiolysis of the ferrous sulfate (Fricke) dosimeter with low-linear energy transfer (LET) radiation have been performed as a function of temperature from 25 to 350C. The predicted yields of Fe oxidation are found to increase with increasing temperature up to 100-150C, and then tend to remain essentially constant at higher temperatures, in very good agreement with experiment. Moreover, the observed dependence of G(Fe) on temperature largely reflects the influence of temperature upon the primary free-radical product yields of the radiolysis, especially the yield of H atoms. Above 200-250C, the more and more pronounced intervention of the reaction of H atoms with water also contributes to the variation of G(Fe), which may decrease or increase slightly, depending on the choice made for the rate constant of this reaction.