Single crystal neutron structure analysis of small organic crystals by complementary use of X-ray and NMR crystallography

X 射线和 NMR 晶体学互补使用小有机晶体的单晶中子结构分析

• 批准号: 20K05470
• 负责人: 大原 高志
• 金额: $ 2.75万
• 依托单位: Japan Atomic Energy Agency
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2020
• 资助国家: 日本
• 起止时间: 2020-04-01 至 2024-03-31
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-20K05470/
• 关键词: 単結晶中性子回折; 有機結晶; J-PARC; 単結晶X線回折; 固体NMR; 量子化学計算

単結晶中性子構造解析法は結晶中の水素原子を観察する極めて強力な手法であるが、巨大単結晶を必要とすることから測定のハードルは非常に高い。本申請課題では、X線回折及び固体NMRで得られた構造情報を最大限活用することで、中性子回折データから決定する必要がある構造情報を極力減らし、これによって従来の1/10程度の体積である0.2～0.3ミリ角の単結晶試料を用いた単結晶中性子構造解析を実現することを目的としている。令和4年度は昨年度に引き続き、構造既知である2-(2'-hydroxyphenyl)benzimidazole (HPBI)について、模擬的に作成した短時間測定データ(1分×15方位)を用いて非水素原子の束縛に用いるX線構造モデルの最適化を試みた。その結果、Hirshfeld Atom Refinement (HAR)もしくは2theta>40°という高角の回折データによる精密化で得られた構造モデルで束縛を掛けることで、束縛無しよりもR因子が向上することが判明し、両手法がX線及び中性子線回折のデータを相補的に用いる上で有効であることを見出した。また、測定時間の短縮は各原子の異方性温度因子が非現実的な値になるという悪影響を及ぼすが、温度因子に対して適切な束縛を掛けることでR値を大きく上げることなく現実的な値となることも確認し、短時間測定の単結晶中性子回折データで構造解析を行う上での束縛の指針を得ることが出来た。また、HPBIの結晶試料の固体NMR測定について、1Hの高分解能スペクトルを得るためにCRAMPS測定を試みた。得られたデータについては、X線及び中性子回折で決定した分子構造からDFT計算の一種であるGIPAW法によって計算した水素原子の化学シフトと比較した上で、構造情報を得るための検討を進めている。

In the analysis method of neutrons in the crystal, the water atom is very important in the analysis of the crystal, and it is necessary to determine the temperature in the crystal. In this application, the problem, X-ray fold and solid NMR are used to obtain the maximum limit for the use of the device. The neutral device determines that it is necessary to create the system. In order to improve the quality of the system, the temperature of the system is 0.2 to 0.3. The results are analyzed by using the crystal neutrons to show the accuracy of the system. In the year of Ling and 4, we introduced the device, built the known device 2-(2'-hydroxyphenyl) benzimidazole (HPBI) generator, and built the module for short-time measurement (1 minute × 15 azimuth). The non-aqueous atomic beam was used to make the most efficient test using the X-ray beam. The results show that Hirshfeld Atom Refinement (HAR) is effective at 40 °. The high angle is high and the precision is accurate. The results show that the R factor is up-to-date, and that the X line and the neutral line are correlated with each other. there is an error in the system. The temperature factor of each atom is measured in short time. The temperature factor is different from the temperature factor. The temperature factor is different. The temperature factor is the temperature factor. The temperature factor is the temperature factor. Short-time measurement of the results of the neutral back-to-back analysis of the analysis of the upper end of the beam indicates that the output is not available. The determination of solid NMR and 1H high decomposition energy of solid NMR and CRAMPS were studied by means of XRD and CRAMPS. The results show that the chemical composition of water atoms is higher than that of water atoms, and the results show that the chemical properties of water atoms are higher than those of water atoms. The results show that the chemical properties of water atoms are higher than those of water atoms, and the chemical properties of water atoms are higher than those of water atoms. The results show that the DFT calculation is accurate.

项目成果

Development of spin-contrast-variation neutron powder diffractometry for extracting the structure factor of hydrogen atoms

用于提取氢原子结构因子的自旋对比变化中子粉末衍射仪的发展

• DOI: 10.1107/s1600576721000303
• 发表时间: 2021
• 期刊: Journal of Applied Crystallography
• 影响因子: 6.1
• 作者: Miura Daisuke;Kumada Takayuki;Sekine Yurina;Motokawa Ryuhei;Nakagawa Hiroshi;Oba Yojiro;Ohhara Takashi;Takata Shin-ichi;Hiroi Kosuke;Morikawa Toshiaki;Kawamura Yukihiko;Ohishi Kazuki;Suzuki Jun-ichi;Miyachi Yoshiyuki;Iwata Takahiro
• 通讯作者: Iwata Takahiro

Insights into Proton Dynamics in a Photofunctional Salt‐Cocrystal Continuum: Single‐Crystal X‐ray, Neutron Diffraction, and Hirshfeld Atom Refinement

深入了解光功能盐共晶连续体中的质子动力学：单晶 X 射线、中子衍射和赫什菲尔德原子细化

• DOI: 10.1002/chem.202103044
• 发表时间: 2022
• 期刊: Chemistry A European Journal
• 作者: Yoshio Yano;Toshikazu Ono;Takashi Ohhara;Yoshio Hisaeda
• 通讯作者: Yoshio Hisaeda

Determination of localized surface phonons in nanocrystalline silicon by inelastic neutron scattering spectroscopy and its application to deuterium isotope enrichment

• DOI: 10.1103/physrevmaterials.5.066003
• 发表时间: 2021-06
• 期刊: Physical Review Materials
• 影响因子: 3.4
• 作者: Takahiro Matsumoto;Ikumi Nomata;T. Ohhara;Y. Kanemitsu

Quantum Proton Entanglement in Nanocrystalline Silicon Surface

纳米晶硅表面的量子质子纠缠

• DOI: 10.1103/physrevb.103.245401
• 发表时间: 2021
• 期刊: Physical Review A
• 影响因子: 2.9
• 作者: Takahiro Matsumoto;Hidehiko Sugimoto;Takashi Ohhara;Stephen M. Bennington;Makoto Tomita;and Susumu Ikeda
• 通讯作者: and Susumu Ikeda

Upgrades of a TOF single-crystal neutron diffractometer SENJU for improvement of versatility

TOF单晶中子衍射仪SENJU的升级以提高多功能性

• 发表时间: 2021
• 作者: Takashi Ohhara;Ryoji Kiyanagi;Akiko Nakao;Koji Munakata;Yoshihisa Ishikawa;Kentaro Moriyama;Itaru Tamura;Koji Kaneko
• 通讯作者: Koji Kaneko