本篇論文是以程序控溫反應/脫附( Temperature-programmed reaction/desorption，TPR/D)和反射式吸收紅外光譜( reflection absorption infrared spectroscopy，RAIRS)技術研究在超高真空系統中FCH2CH2OH及1,4-dioxane在Cu(100)表面上的熱反應與吸附位向。FCH2CH2OH在乾淨Cu(100)表面大部分為可逆分子吸附，且當表面覆蓋量約半層分子(0.5 monolayer)時，約會有20％的FCH2CH2OH分解形成H2O、C2H4及1,4-dioxane。相反地，於吸附有氧原子的Cu(100)表面時，當FCH2CH2OH覆蓋量小於單分子層(monolayer)，FCH2CH2OH會完全分解形成1,4-dioxane及FCH2CH2O(a)中間物，此中間物FCH2CH2O(a)在～160K-220K形成，當表面溫度升高到350K後，此中間物再分解形成FCH2CHO(g)產物。在乾淨Cu(100)表面上，當FCH2CH2OH分子的覆蓋量約0.25 monolayer時，其C-C-O骨架幾乎平行於表面，但隨著曝露量增加到0.5 monolayer時，其C-C-O骨架與表面傾斜；然而在氧化的Cu(100)表面上，FCH2CH2OH分子的覆蓋量約0.25 monolayer時，其C-C-O骨架並不平行於表面。

1,4-dioxane在乾淨Cu(100)表面為可逆性吸附，而且其單層及多層分子性脫附溫度分別在212K、165K。於110K和1.5L 1,4-dioxane(約0.6 monolayer)的曝露量，其環狀結構平行吸附於表面，由2811 cm-1的"軟化"(softened)C-H伸展振動見證了C-H…Cu的交互作用。隨著曝露量增加其環狀結構逐漸地與表面傾斜；當為單分子層的覆蓋量時，估計約有50%的吸附分子傾斜於表面，此單分子層並不是緊密排列地吸附於表面，當表面溫度升高到165K並沒有造成分子的脫附，大部分原本傾斜於表面的分子轉變為平躺於表面的位向。

Temperature-programmed reaction/desorption (TPD/R) and reflection absorption infrared spectroscopy (RAIRS) have been employed to investigate the thermal reactions and adsorption geometry of FCH2CH2OH and 1,4-dioxane molecules on clean and oxygen-preadsorbed Cu(100) surfaces. Molecular desorption predominates in heating FCH2CH2OH adsorbed on clean Cu(100). But ~20% adsorbed FCH2CH2OH molecules at about half monolayer coverage dissociate on the surface to form water, ethylene, and 1,4-dioxane. On the contrary, monolayer FCH2CH2OH completely dissociates on oxidized Cu(100) to form 1,4-dioxane and the surface intermediate of FCH2CH2O(a) which further decomposes to evolve FCH2CHO(g) at temperature higher than ~350 K. The decomposition of FCH2CH2OH to form FCH2CH2O(a) on oxidized Cu(100) begins at ~160 K and is completed prior to 220 K. On clean Cu(100), FCH2CH2OH molecules at ~0.25 monolayer coverage are adsorbed with the C-C-O skeleton approximately parallel to the surface. The C-C-O skeleton tilts away from the surface as the exposure is increased to a half monolayer coverage. However the parallel C-C-O orientation is not observed on the oxidized surface, even at the FCH2CH2OH exposure for a 0.25 monolayer coverage.
1,4-dioxane is adsorbed reversibly on the surface with monolayer desorption at 212 K and multilayer desorption at ～165 K at 4 L exposure. Below ～1.5 L exposure, i.e. 0.6 monolayer coverage, 1,4-dioxane molecules are adsorbed with the ring approximately parallel to the surface. C-H…Cu interaction is evidenced by the C-H vibrational mode softening of 2811 cm-1. Increasing 1,4-dioxane exposure leads to tilted geometry for some of the adsorbed molecules: ～50% at a monolayer coverage at 110 K. However, the monolayer structure is not closely-packed at 110 K, most of the tilted molecules change to flat-lying geometry as the surface temperature is increased to 165 K just prior to the onset of molecular desorption.

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