Competition between Hydrophilic and Argyrophilic Interactions in Surface Enhanced Raman Spectroscopy

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• 作者：John T. Kelly ; Annie K. McClellan ; Lynn V. Joe ; Ashley M. Wright ; Lawson T. Lloyd ; Prof. Gregory S. Tschumper and Prof. Nathan I. Hammer
• 刊名：ChemPhysChem
• 出版年：2016
• 出版时间：September 19, 2016
• 年：2016
• 卷：17
• 期：18
• 页码：2782-2786
• 全文大小：448K
• ISSN：1439-7641

文摘

The competition for binding and charge-transfer (CT) from the nitrogen containing heterocycle pyrimidine to either silver or to water in surface enhanced Raman spectroscopy (SERS) is discussed. The correlation between the shifting observed for vibrational normal modes and CT is analyzed both experimentally using Raman spectroscopy and theoretically using electronic structure theory. Discrete features in the Raman spectrum correspond to the binding of either water or silver to each of pyrimidine's nitrogen atoms with comparable frequency shifts. Natural bond orbital (NBO) calculations in each chemical environment reveal that the magnitude of charge transfer from pyrimidine to adjacent silver atoms is only about twice that for water alone. These results suggest that the choice of solvent plays a role in determining the vibrational frequencies of nitrogen containing molecules in SERS experiments.