Abstract

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.

Department(s)

Chemistry

Publication Status

Full Access

Comments

National Science Foundation, Grant 0955550

Keywords and Phrases

charge transfer; NBO analysis; Raman spectroscopy; SERS; silver island films

International Standard Serial Number (ISSN)

1439-7641; 1439-4235

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 2024 Wiley, All rights reserved.

Publication Date

19 Sep 2016

PubMed ID

27350289

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Chemistry Commons

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