Analysis of electron-molecular vibration interactions in π-electron conjugated radical ion species

π-电子共轭自由基离子物种中电子-分子振动相互作用的分析

• 批准号: 12640486
• 负责人: TASUMI Mitsuo
• 金额: $ 2.3万
• 依托单位: Saitama University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12640486/
• 关键词: Infrared optical fiber; Radical ion; Divalent ion; Infrared absorption spectrum; Conducting polymers; Electron-molecular vibration interaction; ラジカルカチオン; ジカチオン; 有機ラジカルイオン

(1) By using a transmission probe combined with bundles of mid-infrared optical fibers, high-quality infrared spectra have been observed for the radical anion of naphthalene in deuterated tetrahydrofuran and the radical cation of 4,4'-dimethylbiphenyl in deuterated dichloromethane. The transmission probe can be inserted into a glass-tube cell with O-rings under vacuum. Organic radical ions prepared separately in a vacuum system are transferred into the cell for infrared absorption measurements. Observed infrared spectra are in good agreement with calculated spectra based on density functional theory..(2) The molecular structures and infrared absorption and Raman spectra of the neutral species and radical cation of 2,5""-dimethylquinquethiophene and the neutral species and dication of [2.2]quinquethiophenophane were obtained by density functional theory calculations. Strong infrared absorptions characteristic of the dication of [2.2]quinquethiophenophane were calculated. The vibrational modes of these strong infrared absorptions are out-of-phase in the two quinquethiophene parts. The corresponding vibrational modes of the radical cation of 2,5""-dimethyIquinquethiophene have weak infrared absorption intensities.

(1)用透射式探针结合中红外光纤束，观察到萘自由基阴离子在氘代四氢呋喃中和4，4 ′-二甲基联苯自由基阳离子在氘代二氯甲烷中的高质量红外光谱。透射探针可以在真空下插入到具有O形环的玻璃管池中。在真空系统中单独制备的有机自由基离子被转移到用于红外吸收测量的池中。观测到的红外光谱与基于密度泛函理论的计算光谱吻合良好。(2)用密度泛函理论计算了2，5”"-二甲基硫代喹喔啉的中性物种和自由基阳离子以及[2.2]硫代喹喔啉的中性物种和阳离子的分子结构、红外吸收和拉曼光谱。计算了[2.2]五噻吩并菲阳离子的强红外吸收光谱。这些强红外吸收的振动模式在两个五硫键部分中是异相的。2，5”"-二甲基喹硫醚自由基阳离子的相应振动模具有弱的红外吸收强度。

项目成果

Masayuki Nara, Akira Sakamoto, Mitsuo Tasumi ら: "Temperature Dependence of Near-IR Excited Raman Spectra of Crystalline Hen Egg-White Lysozyme"Biopolymers(Biospectroscopy). 62(3). 168-172 (2001)

Masayuki Nara、Akira Sakamoto、Mitsuo Tasumi 等人：“结晶鸡蛋清溶菌酶的近红外激发拉曼光谱的温度依赖性”Biopolymers (Biospectroscopy) 168-172 (2001)。

Masayuki Nara ら: "Temperature Dependence of Near-IR Excited Raman Spectra of Crystalline Hen Egg-White Lysozyme"Biopolymers/Biospectroscopy. 印刷中. (2001)

Masayuki Nara 等人：“结晶鸡蛋清溶菌酶的近红外激发拉曼光谱的温度依赖性”生物聚合物/生物光谱学（2001 年）。

Akira Sakamoto, Mitsuo Tasumi: "Picosecond Time-Resolved Infrared Absorption Studies on the Photoexcited States of Poly(p-phenylenevinylene)"J. Phys. Chem. A. 104. 4198-4202 (2000)

Akira Sakamoto、Mitsuo Tasumi：“聚对亚苯基亚乙烯基光激发态的皮秒时间分辨红外吸收研究”J。

Masayuki Nara, Akira Sakamoto, Mitsuo Tasumi: "Temperature Dependence of Near-IR Excited Raman Spectra of Crystalline Hen Egg-White Lysozyme"Biopolymers (Biospectros copy). 62(3). 168-172 (2001)

Masayuki Nara、Akira Sakamoto、Mitsuo Tasumi：“结晶鸡蛋清溶菌酶的近红外激发拉曼光谱的温度依赖性”生物聚合物（Biospectros 副本）。

A. Sakamoto, M. Tasumi et al.: "Picosecond Time-Resolved Infrared Absorption Studies on the Photoexcited States of Poly(p-phenylenevmylene)"J Phys. Chem. A. 104. 4198-4202 (2000)

A. Sakamoto、M. Tasumi 等人：“聚对亚苯基亚甲基光激发态的皮秒时间分辨红外吸收研究”J Phys。