Construction of a time-resolved multiple resonance spectrometer

时间分辨多重共振光谱仪的构建

• 批准号: 04554016
• 负责人: IKEGAMI Yusaku
• 金额: $ 6.34万
• 依托单位: TOHOKU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research (B)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-04554016/
• 关键词: Time-resolved spectroscopy; Multiple resonance; Electron spin resonace; Photochemical intermediates; Excited states; Electron spin polarization

We built a time-resolved multiple resonance spectrometer equipping a high power raido frequency amplifier (Kalmus 166LPX1, power output : 1 kW (pulse) and 200 W (CW), frequency range : 5-86 MHz) and a synthesizer (Anritsu MG250113, frequency 1-600 MHz). Transient signals are directly taken into a digital storage oscilloscope (Tektronix 2440, DC-100MHz) and a personal computer (Ricoh PS/V2410NAB for data analysis. Both microwave and radio frequency can be applied in the pulse mode by using an X-band pulsed EPR spectrometer (Bruker ESP380E).We applied the system for the measurements of the ENDOR spectra of transient free radicals and the excited triplet states generated by laser pulse irradiation. The present study clearly shows that this system plays an important role in photochemistry, because the spectral resolution is highly improved. The electronic structure and deviation of the geometry in the excited triplet states from the ground state can be clarified from the distribution of the unpaired electron spins. It was shown that spectral sensitivity severely depends on the cavity-helix arrangement. The double resonance technique is complementary to electron spin echo technique, that is, the former is powerful for the strong coupling system between an electron spin and nucleuses while the latter for weak coupling system.

我们建立了一个时间分辨多共振光谱仪，配备了一个高功率雷达频率放大器（Kalmus 166 LPX 1，功率输出：1 kW（脉冲）和200 W（CW），频率范围：5-86 MHz）和一个合成器（Anritsu MG 250113，频率1-600 MHz）。瞬态信号直接输入数字存储示波器（Tektronix 2440，DC-100 MHz）和个人计算机（Ricoh PS/V2410 NAB）进行数据分析。利用X波段脉冲EPR谱仪（Bruker ESP 380 E），在脉冲模式下同时应用微波和射频，测量了瞬态自由基的ENDOR谱和激光脉冲辐照产生的激发三重态。目前的研究清楚地表明，该系统在光化学中起着重要的作用，因为光谱分辨率大大提高。从未成对电子自旋的分布可以阐明激发三重态的电子结构和几何构型偏离基态的情况。结果表明，光谱灵敏度严重依赖于腔螺旋排列。双共振技术与电子自旋回波技术是互补的，前者对电子自旋与原子核之间的强耦合系统很有效，而后者对弱耦合系统很有效。

项目成果

H.Awano,K.Kawase,M.Asai,H.Ohigashi,S.Ohshima,K.Akiyama,M.Kato: "Thin Films of (BEDT-TTF)_2Cu(NSC)_2 Prepared by an Electrodeposition Method" Jpn.J.Appl.Phys.31. 1899-1900 (1992)

H.Awano、K.Kawase、M.Asai、H.Ohigashi、S.Ohshima、K.Akiyama、M.Kato：“通过电镀法制备的 (BEDT-TTF)_2Cu(NSC)_2 薄膜” Jpn。

秋山公男: "有機光化学反応過程での電子スピン分極移動" 反応研報告. 3. 17-32 (1993)

Kimio Akiyama：“有机光化学反应过程中的电子自旋极化转移”反应研究所报告，3. 17-32 (1993)。

K.AKIYAMA,S.TERO-KUBOTA: "Spin Polarization Transfer during Intramolecular Triplet-triplet Energy Transfer as Studied by Time Resolved EPR Spectroscopy" Mol.Phys.83. 1091-1097 (1994)

K.AKIYAMA、S.TERO-KUBOTA：“通过时间分辨 EPR 光谱研究分子内三重态-三重态能量转移过程中的自旋极化转移”Mol.Phys.83。

K.Akiyama,S.Tero-Kubota,: "Spin Polarization Transfer during Intramolecular Triplettriplet Energy Transfer as Studied by Time Resolved EPR Spectroscopy" Mol.Phys.83. 1091-1097 (1994)

K.Akiyama，S.Tero-Kubota，：“通过时间分辨 EPR 光谱研究的分子内三重态能量转移过程中的自旋极化转移”Mol.Phys.83。

Y.Xiao-Zeng,F.Wei-Hai,S.Tero-Kubota: "Substituent Effects on the Zero-field Splitting Constants for the Triplet Ketoamines Generated by Excited State Intramolecular Proton Transfer in Schiff Bases" J.Chem.Soc.,Chem.Commun.20. 2391-2392 (1994)

Y.Xiao-Zeng,F.Wei-Hai,S.Tero-Kubota:“取代基对席夫碱中激发态分子内质子转移产生的三线态酮胺的零场分裂常数的影响”J.Chem.Soc.,