Comparison of experimental and calculated infrared spectra of aminocarbynes on the Pt(111) surface
Comparison of experimental and calculated infrared spectra of aminocarbynes on the Pt(111) surface
复制标题
Pt(111) 表面氨基碳炔的实验红外光谱与计算红外光谱的比较
DOI：
--
复制
发表时间：
2003
期刊：
影响因子：
--
通讯作者：
M. Trenary
中科院分区：
文献类型：
--
作者：
Bappaditya Chatterjee;D. Kang;E. Herceg;M. Trenary
利用密度泛函理论计算了Pt、Pt7H6、Pt2、Pt9H14和Pt4簇上的CNH2、CNHCH3和CN(CH3)2三种氨基羰基化合物CNH2、CNHCH3和CN(CH3)2的红外光谱，并与Pt（111）表面的实验光谱进行了比较。不同的簇提供了吸附模型在顶部，双桥和三桥的位置。对于双桥站点的Pt2和Pt9H14模型，计算成功地再现了观测到的13C、15N和D替换的频移，并且与观测到的相对强度基本一致。在CNHCH3的情况下，两种可能的构象中的一种的计算结果与实验光谱更吻合。更大的Pt9H14星团与Pt2模型相比没有得到改善，这表明后者星团的实验光谱与计算光谱之间的差异不是由于有限的星团大小效应。计算了不同吸附位点模式下的光谱。
Infrared spectra of the three aminocarbynes CNH2, CNHCH3, and CN(CH3)2 attached to Pt, Pt7H6, Pt2, Pt9H14, and Pt4 clusters are calculated from density functional theory and compared with the corresponding experimental spectra measured on the Pt(111) surface. The different clusters provide models for adsorption at on-top, twofold bridge, and threefold bridge sites. For the Pt2 and Pt9H14 models of the twofold bridge site, the calculations successfully reproduce the observed frequency shifts for 13C, 15N, and D substitutions and yield fair agreement with the observed relative intensities. In the case of CNHCH3, the calculations for one of two possible conformers give better agreement with the experimental spectra. No improvement was achieved with the larger Pt9H14 cluster compared with the Pt2 model, indicating that the differences between the experimental and calculated spectra for the latter cluster were not due to finite cluster size effects. The calculated spectra for the different adsorption site mode...