Department of Chemistry, Sookmyung Women's University, Seoul 140-742, Republic of Korea.
Phys Chem Chem Phys. 2013 Oct 21;15(39):16594-8. doi: 10.1039/c3cp52760c. Epub 2013 Aug 20.
We confirmed the coverage dependent variation of tautomers of 2-mercaptothiazoline (the thiolate and thione forms) adsorbed on the Ge(100) surface under UHV conditions by using HRXPS measurements in conjunction with the DFT calculation method, which was studied before only in aqueous systems. The C 1s, S 2p, and N 1s core-level spectra obtained using HRXPS revealed the simultaneous presence of two distinct adsorption structures in different proportions at both low (0.15 ML) and high (0.65 ML) coverages. Moreover, we modelled the adsorption structures and geometric configurations of the bond states of 2-mercaptothiazoline on the Ge(100) surface by using the DFT calculation method, and found that the S dative bonded structure is the most stable adsorption structure for the thione form of 2-mercaptothiazoline and that the S-H dissociated-N dative bonded structure is the most stable adsorption structure for the thiolate form.
我们通过使用高分辨率 X 射线光电子能谱（HRXPS）测量与之前仅在水相体系中研究过的密度泛函理论（DFT）计算方法相结合，证实了在 UHV 条件下吸附在 Ge(100)表面的 2-巯基噻唑啉（硫醇和硫酮形式）的互变异构体的覆盖度依赖性变化。使用 HRXPS 获得的 C 1s、S 2p 和 N 1s 芯能级谱表明，在低（0.15 ML）和高（0.65 ML）覆盖度下，两种不同比例的两种不同吸附结构同时存在。此外，我们通过 DFT 计算方法模拟了 2-巯基噻唑啉在 Ge(100)表面的吸附结构和键态的几何构型，发现对于 2-巯基噻唑啉的硫酮形式，S 给予键合结构是最稳定的吸附结构，而对于 2-巯基噻唑啉的硫醇形式，S-H 解离-N 给予键合结构是最稳定的吸附结构。
