Formation of stable nitrene surface species by the reaction of adsorbed phenyl isocyanate at the Ge(100)-2 × 1 surface.
Formation of stable nitrene surface species by the reaction of adsorbed phenyl isocyanate at the Ge(100)-2 × 1 surface.
复制标题
通过吸附在 Ge(100)-2 × 1 表面的异氰酸苯酯反应形成稳定的氮烯表面物种。
作者：
K. Wong;Jukka T. Tanskanen;S. Bent
采用傅里叶变换红外光谱（FTIR）、X射线光电子能谱（XPS）、程序升温脱附、量子化学计算和分子动力学模拟等方法，对异氰酸苯酯（PIC）在Ge（100）-2 × 1表面吸附后的反应进行了实验和理论研究. PIC最初通过[2 + 2]环加成吸附在异氰酸酯的C = N键上，如前所述，但该初始产物在室温下以分钟的时间尺度转化为第二产物。实验和理论计算结果表明，生成的第二种产物是苯基氮烯（C6 H5 N），它通过Ge-N单键共价键合在锗表面上。这一结论得到了FTIR光谱实验和使用苯基异氰酸酯-（15）N和苯基-d5异氰酸酯的密度泛函理论计算的进一步支持。
The reaction of phenyl isocyanate (PIC) following adsorption at the Ge(100)-2 × 1 surface has been investigated both experimentally and theoretically by Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy, temperature-programmed desorption, quantum chemical calculations, and molecular dynamics simulations. PIC initially adsorbs by [2 + 2] cycloaddition across the C═N bond of the isocyanate, as previously reported, but this initial product converts to a second product on the time scale of minutes at room temperature. The experimental and theoretical results show that the second product formed is phenylnitrene (C6H5N) covalently bonded to the germanium surface via a single Ge-N bond. This conclusion is further supported by FTIR spectroscopy experiments and density functional theory calculations using phenyl isocyanate-(15)N and phenyl-d5 isocyanate.