台日國合計畫---各種紅外光譜技術在不穩定分子之鑑識及動態學的應用

Abstract

此三年計劃係以各種尖端技術研究不穩定分子的紅外光譜學及其相關 化學動態學，共分為七個部分：(1)以步進式時間解析霍氏放光光譜法研究 分子光解動態學，測量產物的內能分佈；擬研究的分子有chloropropene 或 allyl chloride，acetophenone 或benzaldehyde，NO2 或nitromethane；(2)以步 進式時間解析霍氏放光光譜法研究雙分子反應的化學動態學，擬研究的反 應有：Cl +振動激發的CH3OH 或HCOOH，O(1D) +CS2 或OCS，及 O(1D)+NO；(3)以步進式時間解析霍氏吸收光譜法研究反應中間物之紅外吸 收光譜；擬研究的分子有：CH3SO 或CH3SOO，CH3CO 或C6H5CO，C6H5OO； (4)小分子在p-H2 間質的轉動、反轉及內轉動；擬探討的分子有：C2H4，NH3 及C2H6；(5)利用間質隔離法，產生新穎分子並以紅外吸收光譜及理論化學 計算鑑識之；擬研究的分子有CH3S，ClCS2 或ClOCS 及其異構物， Cl+HCOOH 之生成物； (6)發展以真空紫外光/紅外光游離法研究自由基之 紅外光譜法，初步擬架設新系統，並研究超音射束中的CH3S 及C2H3 之紅 外光譜； (7) 發展凝態的紅外光譜技術－ 包括薄膜的紅外光 electroabsorption，薄膜的瞬態產物偵測以及以ATR 測量薄膜的技術，並研 究linked pyrene 薄膜在高電場或光激發之行為以瞭解electroluminescence 之 機制。

This three-year proposal focuses on IR spectroscopy and dynamics of unstable species. It consists of seven parts: (1) Use step-scan time-resolved Fourier-transform spectroscopy in emission mode to investigate photodissociation dynamics by determining internal energy distributions of photofragments. Species to be studied include chloropropene or allylchloride, acetophenone or benzaldehyde, NO2 or nitromethane; (2) Use step-scan time-resolved Fourier-transform spectroscopy in emission mode to investigate dynamics of bimolecular reactions, including reactions of Cl with vibrationally excited CH3OH or HCOOH, reactions of O(1D) with CS2 or OCS, and O(1D)+NO; (3) Use step-scan time-resolved Fourier-transform spectroscopy in absorption mode to investigate IR absorption of reaction intermediates, such as CH3SO or CH3SOO, CH3CO or C6H5CO, and C6H5OO; (4) Use p-H2 as a matrix host to explore rotation, internal rotation, and inversion of small molecules such as C2H4, C2H6, and NH3; (5) Use matrix effect to produce novel species and to characterize them with IR absorption and quantum-chemical calculations. Species of interest are CH3S, isomers of ClCS2 or ClOCS, and products of Cl + HCOOH; (6) Set up a system using VUV/IR ionization detection to develop IR spectral techniques of unstable species, such as CH3S and C2H3; (7) Develop IR spectral techniques for condensed matters, including electroabsorption of thin film, transient detection of thin film, and ATR for thin film under intense electric field.