Premium
A joint experimental and theoretical Raman study on the interactions of pyridine adsorbed on chemically pure Ag 18 clusters
Author(s) -
An Pan,
Wu Haiming,
Pembere Anthony M.S.,
Luo Zhixun
Publication year - 2019
Publication title -
journal of raman spectroscopy
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.748
H-Index - 110
eISSN - 1097-4555
pISSN - 0377-0486
DOI - 10.1002/jrs.5653
Subject(s) - pyridine , raman scattering , polarizability , raman spectroscopy , chemistry , density functional theory , natural bond orbital , nanoclusters , chemical physics , relaxation (psychology) , photochemistry , molecular physics , analytical chemistry (journal) , computational chemistry , molecule , organic chemistry , optics , psychology , social psychology , physics
The interaction of pyridine–Ag has been a hot topic since the finding of surface‐enhanced Raman scattering; however, there is still challenge to accurately evaluate the interactions within nano‐systems. Here we have synthesized chemically pure Ag 18 nanoclusters by a facile method based on laser ablation in liquid and conducted a joint experimental and theoretical Raman spectroscopic study for pyridine adsorbed on the specific‐sized Ag clusters. As a result, altered Raman feature for the pyridine‐Ag 18 system in contrast to pure pyridine is observed shedding light on the charge‐transfer interactions between pyridine and Ag. Utilizing natural population analysis, we studied the charge distribution before and after pyridine adsorbed on the Ag 18 cluster. Also, we calculated static polarizability components and isotropic polarizability of pyridine and the pyridine‐Ag 18 complex and studied the donor‐acceptor orbital overlaps via natural bond orbital analysis, charge decomposition analysis, electron density difference analysis, and density of state analysis. Such a comprehensive and semiquantitative study provides firm evidence for the chemical mechanism in surface‐enhanced Raman scattering theory.