Electronic Spectra of Aliphatic Carbonyls and Electron-phonon Couplings.

脂肪族羰基和电子声子耦合的电子光谱。

• 批准号: 05640573
• 负责人: KOYANAGI Motohiko
• 金额: $ 1.34万
• 依托单位: KYUSHU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05640573/
• 关键词: acetone; hexachloroacetone; photolysis at low temperature; benzyl radical; heat-pulse spectra; 芳香族カルボニル; 電子-フォノン相互作用; 極低温光反応; ラジカル反応

Rigid matrices of aliphatic mono-carbonyls, such as acetone and acetoal-dehyde, generally give rise to very diffuse emission and absorption bands even at 4.2 k. No well-developped spectra have so far been reported except for the T-S absorption and emission spectra of hexachloroacetone in the crystal (M.KoyanGII et al., Chem.Phys., 5,107 (1974)). The main reason for this difficulty may greatly be attributed to inhomogeneous broadening whose origins are due to many geometrically different sites in one part and impurities produced during light irradiation in another part. The present work started with a plan that the latter problem was diminished as best as possible. For this purpose, crystal samples of mono-carbonyls at 4.2 k were lifted up at a speed of about 5 mm per minute using a synchronous motor during the optical measurements. This worked in part for acetone crystals : a band with a spacing of 300-400cm^<-1> was clearly observed. Technical difficulties coming from using such a large sample cell(50mm phi x 100mum), fluctuation of the sample cell, helium bubbling, etc. prevented us from ob-serving good S/N signals. Apart from this partial success, a well-developed S_1*S_0 absorption spectrum of hexachloroacetone was observed similarly. Asystematic series of research on the benzyl radical in the rigid matrices were very useful for us to take into account the role of impurities produced upon light irradiation in the host system.

脂肪族单羰基的刚性基质，如丙酮和乙醛，即使在4.2K也通常产生非常弥散的发射和吸收带。除了晶体中六氯丙酮的T-S吸收和发射光谱(M.KoyanGii等，Chem.Phys.，5,107(1974))，迄今还没有报道。造成这一困难的主要原因可以很大程度上归因于非均匀展宽，其起源是由于在一个部分中有许多几何上不同的位置，以及在另一部分中在光照射下产生的杂质。目前的工作始于一项计划，即尽可能减少后一个问题。为此，在光学测量过程中，用同步电机以每分钟约5毫米的速度提升4.2K下的单羰基晶体样品。这在一定程度上适用于丙酮晶体：清晰地观察到一条间距为300-400 cm^-1的带。使用这么大的样品盒(50 mm×100微米)带来的技术困难、样品盒的波动、氦的鼓泡等使我们无法观测到良好的S/N信号。除了这一部分成功外，还观察到了六氯丙酮的S_1*S_0吸收光谱。对刚性基质中的苄基自由基进行了一系列系统的研究，对于我们考虑光照射产生的杂质在主体体系中的作用是非常有用的。

项目成果

K.Kosugi, K.Uejoh, and M.Koyanagi: "Characteristic Fluorescence Band Patterns of the Benzyl Radical in Polymorphous Cyclo-hexane Matrices at Low Temperature." Memors of the Faculty of Science, Kyushu University, Ser.C. 19. 97-104 (1994)

K.Kosugi、K.Uejoh 和 M.Koyanagi：“低温下多晶型环己烷基质中苄基自由基的特征荧光带模式”。

K.Kosugi et al.: "Characteristic Fluorescence Band Patterns of the Benzvl Radical in Amorphous Cyclohexane Matrices" Mem.Fac.Sci.,Kyushu Univ.,Ser.C,. 19. 97-104 (1994)

K.Kosugi 等人：“无定形环己烷基质中 Benzvl 自由基的特征荧光带模式”Mem.Fac.Sci.，九州大学，Ser.C，。

K.Uejoh and M,Koyanagi: "Mechnism of the benzyl radical Formation from Toluene in Rigid Matrices at Low Temperature." Memors of the Faculty of Science, Kyushu University, Ser.C. 19. 7-14 (1993)

K.Uejoh 和 M,Koyanagi：“低温刚性基质中甲苯形成苄基自由基的机制”。

K.Uejoh and M.Koyanagi: "Benzyl Radical Formation and Its Fluores-cence Spectrum in Toluene Crystals at Low Temperature." Memors of the Faculty of Science, Kyushu University, Ser.C. 19. 105-108 (1994)

K.Uejoh 和 M.Koyanagi：“低温甲苯晶体中苄基自由基的形成及其荧光光谱”。

K.Uejoh et al.: "Benzyl Radical Formation and Its Fluorescence Spectru in Toluene Crystals at Low Temperature" Mem.Fac.Sci.,Khyshu Univ.,Ser.C,. 19. 105-108 (1994)

K.Uejoh 等人：“低温甲苯晶体中的苄基自由基形成及其荧光光谱”Mem.Fac.Sci.，Khyshu Univ.，Ser.C，。