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Direct Visualization of the Chemical Mechanism in SERRS of 4-Aminothiophenol/Metal Complexes and Metal/4-Aminothiophenol/Metal Junctions

Sun, Mengtao LU and Xu, Hongxing LU (2009) In ChemPhysChem 10(2). p.392-399
Abstract
We theoretically investigate the mechanism of chemical enhancement of surface-enhanced resonance Roman scattering (SERRS) of para-aminothiophenol (PATP)/metal complexes and metal/PATP/metal junctions. The method of charge difference density is used to visualize intracluster excitation and charge transfer (CT) between PATP and metal during the process of resonant electronic transitions. It is found that the selective enhancement of the b(2) mode in SERRS spectra result not only from Albrecht's A term (the Frank-Condon term), but also from the Herzberg-Teller term (Albrecht's B mechanism) via resonant CT For the metal/PATP/metal junctions, the calculated results reveal that the Roman spectrum is of SERRS nature and the nontotally symmetric... (More)
We theoretically investigate the mechanism of chemical enhancement of surface-enhanced resonance Roman scattering (SERRS) of para-aminothiophenol (PATP)/metal complexes and metal/PATP/metal junctions. The method of charge difference density is used to visualize intracluster excitation and charge transfer (CT) between PATP and metal during the process of resonant electronic transitions. It is found that the selective enhancement of the b(2) mode in SERRS spectra result not only from Albrecht's A term (the Frank-Condon term), but also from the Herzberg-Teller term (Albrecht's B mechanism) via resonant CT For the metal/PATP/metal junctions, the calculated results reveal that the Roman spectrum is of SERRS nature and the nontotally symmetric b(2) mode is strongly enhanced at the incident wavelength of 1064 nm when Au and Ag nanoparticles are the first and second layer, respectively, and the dominant enhancement mechanism is the Herzberg-Teller term in chemical enhancement via tunneling charge transfer (intervalence electron transfer from the Ag cluster to the Au cluster). When the first and second layers were inverted (i.e. the Ag and Au nanoparticles are the first and second layers, respectively), the Roman spectrum at on incident wavelength of 1064 nm is due to normal Roman scattering, and the nontotally symmetric b(2) mode is not strongly enhanced. Our theoretical results not only support the experimental findings, but also provide a clear physical interpretation. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
surface-enhanced resonance, Raman spectroscopy, charge transfer, density functional calculations
in
ChemPhysChem
volume
10
issue
2
pages
392 - 399
publisher
John Wiley & Sons
external identifiers
  • wos:000263372400014
  • scopus:59449087187
ISSN
1439-7641
DOI
10.1002/cphc.200800596
language
English
LU publication?
yes
id
a7313e48-8482-4dc7-953b-384eb9da3277 (old id 1372534)
date added to LUP
2009-05-08 13:32:09
date last changed
2017-12-10 03:53:18
@article{a7313e48-8482-4dc7-953b-384eb9da3277,
  abstract     = {We theoretically investigate the mechanism of chemical enhancement of surface-enhanced resonance Roman scattering (SERRS) of para-aminothiophenol (PATP)/metal complexes and metal/PATP/metal junctions. The method of charge difference density is used to visualize intracluster excitation and charge transfer (CT) between PATP and metal during the process of resonant electronic transitions. It is found that the selective enhancement of the b(2) mode in SERRS spectra result not only from Albrecht's A term (the Frank-Condon term), but also from the Herzberg-Teller term (Albrecht's B mechanism) via resonant CT For the metal/PATP/metal junctions, the calculated results reveal that the Roman spectrum is of SERRS nature and the nontotally symmetric b(2) mode is strongly enhanced at the incident wavelength of 1064 nm when Au and Ag nanoparticles are the first and second layer, respectively, and the dominant enhancement mechanism is the Herzberg-Teller term in chemical enhancement via tunneling charge transfer (intervalence electron transfer from the Ag cluster to the Au cluster). When the first and second layers were inverted (i.e. the Ag and Au nanoparticles are the first and second layers, respectively), the Roman spectrum at on incident wavelength of 1064 nm is due to normal Roman scattering, and the nontotally symmetric b(2) mode is not strongly enhanced. Our theoretical results not only support the experimental findings, but also provide a clear physical interpretation.},
  author       = {Sun, Mengtao and Xu, Hongxing},
  issn         = {1439-7641},
  keyword      = {surface-enhanced resonance,Raman spectroscopy,charge transfer,density functional calculations},
  language     = {eng},
  number       = {2},
  pages        = {392--399},
  publisher    = {John Wiley & Sons},
  series       = {ChemPhysChem},
  title        = {Direct Visualization of the Chemical Mechanism in SERRS of 4-Aminothiophenol/Metal Complexes and Metal/4-Aminothiophenol/Metal Junctions},
  url          = {http://dx.doi.org/10.1002/cphc.200800596},
  volume       = {10},
  year         = {2009},
}