Adsorption, Chemical Enhancement, and Low-Lying Excited
States of p‑Methylbenzenethiol on Silver and
Gold Nanoparticle Surfaces: A Surface Enhanced Raman Spectroscopy
and Density Functional Theory Study
Posted on 2019-09-09 - 16:35
Adsorption
and chemical enhancement of p-methylbenzenethiol
(PMBT) on silver and gold nanoparticle surfaces have been studied
using surface enhanced Raman spectroscopy (SERS) and density functional
theory (DFT) calculations. In normal Raman spectra, the Raman intensity
of the molecule is sensitive to methyl substitution at the para position.
DFT calculations for the Raman spectrum of PMBT reproduces well the
Raman spectrum in nonpolar solution relative to PMBT in powder. This
accords with the order of the PMBT molecules in the solid. The SERS
results of PMBT adsorbed on Au and Ag nanoparticles indicate that
the Raman intensity in the low-wavenumber region increases with increasing
excitation wavelength. The electronic structures of low-lying excited
states have been explored for this increase in different PMBT-S-metal
cluster complexes. DFT results indicate that low-energy excited states
are in fact present and originate from two types of excitations, one
localized at the sulfur–silver/gold bonding region and another
one from a charge transfer state excited from PMBT to the silver and
gold surfaces. Both interfacial excited states contribute significantly
to the chemical enhancement mechanism and change relative Raman intensities
of adsorbed PMBT. The chemical bonding interaction and the interfacial
energy level alignment are therefore important to understand SERS
processes of PMBT adsorbed on noble metal surfaces of nanostructures.
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Wang, Rui; Shen, Xiao-Ru; Zhang, Meng; Devasenathipathy, Rajkumar; Pang, Ran; Wu, De-Yin; et al. (2019). Adsorption, Chemical Enhancement, and Low-Lying Excited
States of p‑Methylbenzenethiol on Silver and
Gold Nanoparticle Surfaces: A Surface Enhanced Raman Spectroscopy
and Density Functional Theory Study. ACS Publications. Collection. https://doi.org/10.1021/acs.jpcc.9b06431
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AUTHORS (9)
RW
Rui Wang
XS
Xiao-Ru Shen
MZ
Meng Zhang
RD
Rajkumar Devasenathipathy
RP
Ran Pang
DW
De-Yin Wu
JZ
Jingdong Zhang
JU
Jens Ulstrup
ZT
Zhong-Qun Tian
KEYWORDS
low-wavenumber region increasesDensity Functional Theory Study AdsorptionGold Nanoparticle SurfacesLow-Lying Excited StatesSERSenergy level alignmentchemical enhancement mechanismcharge transfer stategold nanoparticle surfacesRaman intensitySurface Enhanced Raman SpectroscopyDFTRaman spectrumPMBT-S-metal cluster complexes