Infrared-based and Raman-based Observation of Molecular Vibrations towards Physicochemical Analysis of Ionic Liquids

基于红外和拉曼的分子振动观察对离子液体的物理化学分析

• 批准号: 14340190
• 负责人: ONISHI Hiroshi
• 金额: $ 6.53万
• 依托单位: Kanagawa Academy of Science and Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14340190/
• 关键词: Ionic liquids; Solvents; Green chemistry; Sum-frequency spectroscopy; Fourth-order Raman spectroscopy; Interface; Molecular Structure; Time-domain spectroscopy; 赤外分光; 液体表面

Two non-linear, time-domain Raman methods have been developed towards physicochemical analysis of ionic liquids.(1)Interface-specific observation of molecular vibrations was achieved with visible light by a fourth-order optical process. An aqueous solution of oxazine dye interfaced with air was irradiated with 16-fs pluses at 600 nm. A pump pulse excited Raman-active nuclear motions of the dye. A probe pulse interacted with the excited molecules to generate second harmonic light, the intensity of which was oscillated as a function of the pump-probe delay. Fourier-transformation of the oscillation provided a vibrational spectrum of 0 - 1000 cm^<-1> for the dye located at the air-solution interface.(2)Femtosecond time-resolved photoinduced reflectivity change was measured for the first time on a spincoated dye (cresyl violet) of submonolayer coverage on a fused silica substrate. We found that the sensitivity of the reflection measurement was much higher than that of the absorption measurement for thin monolayers of dye. A prominent beating structure due to vibrational coherence of the dye was observed on the time-resolved reflection signal. A vibrational spectrum of the dye at submonolayer coverage, which corresponded its resonance Raman spectrum, was obtained in the range of 0-800 cm^<-1> by a Fourier transform analysis of the reflection signal.

两种非线性时域拉曼方法被用于离子液体的物理化学分析。(1)通过四阶光学过程，利用可见光实现了分子振动的界面特异性观测。用16-fs +在600 nm处照射恶嗪染料与空气界面的水溶液。一个泵浦脉冲激发了染料的拉曼活性核运动。探针脉冲与受激分子相互作用产生二次谐波光，其强度随泵浦-探针延迟的变化而振荡。振荡的傅里叶变换为位于空气-溶液界面的染料提供了0 - 1000 cm^<-1>的振动谱。(2)首次在熔融二氧化硅衬底上测量了亚单层覆盖的纺涂染料（甲酚紫）的飞秒时间分辨光致反射率变化。我们发现，对于薄单层染料，反射测量的灵敏度远远高于吸收测量。由于染料的振动相干性，在时间分辨反射信号上观察到明显的跳动结构。在0 ~ 800 cm^<-1>范围内，通过对反射信号的傅里叶变换分析，得到了染料在亚单层覆盖下的振动谱，与共振拉曼光谱相对应。

项目成果

Takeshita, Sasaki, Kobashi, Tanaka, Maeda, Yamakata, Ishibashi, Onishi: "Photophysics and Electron Dynamics in Dye-sensitized Semiconductor Film Studied by Time-resolved Mid-IR Spectroscopy"Journal of Physical Chemistry B. 107(In press). (2003)

Takeshita、Sasaki、Kobashi、Tanaka、Maeda、Yamakata、Ishibashi、Onishi：“通过时间分辨中红外光谱研究的染料敏化半导体薄膜中的光物理学和电子动力学”物理化学杂志 B.107（出版中）。

山方啓, 石橋孝章, 大西洋: "時間分解赤外分光でみた二酸化チタン微粒子から吸着分子への電荷移動"表面科学. 24. 46-52 (2003)

Kei Yamakata、Takaaki Ishibashi，Atlantic：“通过时间分辨红外光谱观察到从二氧化钛细颗粒到吸附分子的电荷转移”表面科学 24. 46-52 (2003)。

A multiplex infrared-visible sum-frequency spectrometer with wavelength tunability of the visible probe

可见光探头波长可调的复合红外-可见光和频光谱仪

• 发表时间: 2002
• 期刊: Applied Physics Letters 81
• 作者: Taka-aki Ishibashi;Hiroshi Onishi
• 通讯作者: Hiroshi Onishi

石橋孝章, 大西 洋: "マルチプレックス赤外可視和周波発生分光法とその有機単分子膜への応用"真空. (印刷中). (2004)

Takaaki Ishibashi、Hiroshi Onishi：“多重红外-可见光和频发生光谱及其在有机单层中的应用”真空（2004 年出版）。

石橋孝章, 大西 洋: "可視プローブ波長可変性を持つマルチプレックス赤外可視和周波発生分光装置の開発"表面科学. 23. 468-474 (2002)

Takaaki Ishibashi、Hiroshi Onishi：“具有可见光探头波长可调性的多重红外-可见光和频发生光谱仪的开发”表面科学 23. 468-474 (2002)。