| Project/Area Number |
07454152
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Physical chemistry
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| Research Institution | KYUSHU UNIVERSITY |
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Principal Investigator |
TANAKA Takehiko Kyushu U., Fac.of Science, Professor, 理学部, 教授 (00011586)
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| Co-Investigator(Kenkyū-buntansha) |
IMAJO Takashi Kyushu U., Fac.of Science, Research Associate, 理学部, 助手 (40213227)
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| Project Period (FY) |
1995 – 1996
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| Project Status |
Completed (Fiscal Year 1996)
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| Budget Amount *help |
¥8,000,000 (Direct Cost: ¥8,000,000)
Fiscal Year 1996: ¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1995: ¥5,900,000 (Direct Cost: ¥5,900,000)
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| Keywords | time-resolved spectroscopy / ultraviolet photolysis / infrared semiconductor laser / reaction rate / FeCO radical / Fe(CO)_2 radical / Fe(CO)_5 / 時間分解赤外半導体レーザー分光 / 紫外レーザー光解離 / CO / CS_2 / 時間分解半導体レーザー分光 / 赤外ダイオードレーザー分光 / シリレンラジカル / SiHラジカル |
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| Research Abstract |
The aim of this project is to investigate chemical reactions of free radicals generated by ultra-violet laser photolysis by applying highly sensitive time-resolved infrared semiconductor laser spectroscopy. Precursor molecules flowing through an absorption cell of about 2 m length are photolyzed by excimer laser pulses, and generated free radicals are monitored by an infrared semiconductor laser beam, which multipasses a White-type optics. The output of an infrared detector is A/D converted and sent to a personal computer, which performs dual-gated integration and time-profile accumulation.This apparatus was used to observe vibration-rotation spectra in the 5mum region of the FeCO and Fe(CO)_2 radicals generated by ArF excimer laser photolysis of Fe(CO)_5. For FeCo, detailed spectral assignment was accomplished, resulting in precise spectroscopic constants. Absorption lines of Fe(CO)_2 were also identified.
These data were utilized for the measurement of decay curves of the FeCO and Fe(CO)_2 radicals, from which rate constants (in units of cm^3 molec^<-1> sec^<-1>) were derived as 1.25(5)*10^<-10> and 1.76(10)*10^<-10> for reactions of the respective radicals with the precursor Fe(CO)_5. Measurement was also made for systems with mixed gases, CO,CS_2, and (CN)_2, and reaction rates with these reactants were determined. The rate of the reaction with CO is 1.48(5)*10^<-11> for FeCo and 1.77(21)*10^<-11> for Fe(CO)_2. The radicals react with CO at an order of magnitude slower rate than with the precursor. The reaction rate with CS_2 is 2.87(24)*10^<-10> for FeCO and 1.69(15)*10^<-10> for Fe(CO)_2. FeCO reacts with (CN)_2 at a rate of 2.19(22)*10^<-10> and Fe(CO)_2 at 1.96(17)*10^<-10>. These reaction rates are comparable with those with the precursor.
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