论文标题
XANES光谱法的模拟和AU上N-杂环卡宾斯的总能量的计算（111）
Simulation of XANES spectroscopy and the calculation of total energies for N-heterocyclic carbenes on Au(111)
论文作者
论文摘要
最近已经证明，N-杂环卡宾斯（NHC）在金属表面上形成自组装的单层（SAM）。因此，重要的是要表征和理解其结合模式以完全利用功能表面系统中的NHC。为了协助这项工作，我们对NHC（111）上的NHC进行了{\ it First-principles}的总能量计算，并在边缘结构（XANES）附近的X射线吸收模拟。我们考虑的NHC是N，N-二甲基 - ，N，N-二乙基，N，N-二甲丙基苯甲酰氮二唑基二氮基（$^b $ nhc $^x $，分别为X = me，et和ipr）和bis-$^b $ nhc nhc $ nhc $^x $ coblesees with aueles cartery aueles。我们对$^b $ nhc $^x $的能量稳定性和au（111）的复合物的能量稳定性进行了全面分析，对于前者，我们介绍了机翼组在确定附件几何形状中的作用。通过计算氮K边缘X射线吸收光谱来进行进一步的结构表征。我们的模拟XANES结果可以深入了解（i）$^b $ nhc $^x $/au几何形状与N（$ 1S $）$ \ rightArrow $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ y ast/σ^\ ast $，pre-Edge/of-Edge/of-Edge/of-Edge/of-Edge/of-Edge/near-Edge，吸收强度和（II）的贡献，以及（ii）X。 光谱。将我们的模拟与最近的实验结果进行了比较。
It has recently been demonstrated that N-heterocyclic carbenes (NHCs) form self-assembled monolayers (SAMs) on metal surfaces. Consequently, it is important to both characterize and understand their binding modes to fully exploit NHCs in functional surface systems. To assist with this effort, we have performed {\it first-principles} total energy calculations for NHCs on Au(111) and simulations of X-ray absorption near edge structure (XANES). The NHCs we have considered are N,N-dimethyl-, N,N-diethyl-, N,N-diisopropylbenzimidazolylidene ($^B$NHC$^X$, with X=Me, Et, and iPr, respectively) and the bis-$^B$NHC$^X$ complexes with Au derived from these molecules. We present a comprehensive analysis of the energetic stability of both the $^B$NHC$^X$ and the complexes on Au(111) and, for the former, examine the role of the wing group in determining the attachment geometry. Further structural characterization is performed by calculating the nitrogen K-edge X-ray absorption spectra. Our simulated XANES results give insight into (i) the relationship between the $^B$NHC$^X$/Au geometry and the N($1s$) $\rightarrow$ $π^\ast/σ^\ast$, pre-edge/near-edge, absorption intensities, and (ii) the contributions of the molecular deformation and molecule-surface electronic interaction to the XANES spectrum. Our simulations are compared with recent experimental results.
