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Roles of Plasmonic Excitation and Protonation on Photoreactions of p-Aminobenzenethiol on Ag Nanoparticles
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.ORCID iD: 0000-0002-3282-0711
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.ORCID iD: 0000-0003-0007-0394
2014 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 118, no 13, 6893-6902 p.Article in journal (Refereed) Published
Abstract [en]

There is increasing evidence that surface plasmons could catalyze photochemical reactions of organic molecules on metal surfaces. However, due to the complex interactions among the substrate, the adsorbate, the environment, and the incident light, the existence and the underlying mechanism of such catalytic processes have been under intense debate. Here we present a systematic first principles study on one of the most studied and controversial systems, namely, p-aminobenzenethiol (PATP) adsorbed on silver nanoparticles. Our calculations have confirmed that the observed surface-enhanced Raman scattering (SERS) bands at 1142, 1391, and 1440 cm(-1) of PATP on silver surfaces belong to its coupling reaction product, 4,4'-dimercaptoazobenzene (DMAB). It is found that the deprotonation or protonation of N atoms is the key initial step for the transformations between PATP and DMAB. The photodecomposition reaction from DMAB to PATP can occur only under the conditions that both proton transfer and plasmonic excitations have taken place. Moreover, in addition to the widely suggested hot-electron injection mechanism of plasmon, a new photochemical channel has been revealed in the decomposition of DMAB molecules under suitable incident light. This may open up an entire new type of chemical reaction in surface chemistry that we call plasmonic photochemistry. Our theoretical calculations provide consistent interpretations for the experimentally observed pH-,wavelength-,and electrode potential dependence of the SERS spectra of PATP/DMAB adsorbed on silver surfaces. Our findings highlight the important role of theoretical investigations for better understanding of complex processes involved in photochemical reaction of surface adsorbates.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2014. Vol. 118, no 13, 6893-6902 p.
Keyword [en]
Electrode potentials, First-principles study, Photo-decomposition, Silver nanoparticles, Surface adsorbates, Surface enhanced Raman Scattering (SERS), Theoretical calculations, Theoretical investigations
National Category
Physical Chemistry
URN: urn:nbn:se:kth:diva-145587DOI: 10.1021/jp500728sISI: 000334258600040ScopusID: 2-s2.0-84898077395OAI: diva2:719286

QC 20140523

Available from: 2014-05-23 Created: 2014-05-23 Last updated: 2016-04-29Bibliographically approved
In thesis
1. Theoretical Study on Chemical Structures and Stability of Molecules in Metallic Junctions
Open this publication in new window or tab >>Theoretical Study on Chemical Structures and Stability of Molecules in Metallic Junctions
2016 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

In this thesis, we focus on the structural identification of the interface using surface enhanced Raman spectroscopy (SERS) and inelastic electron tunnelling scattering (IETS). Two different molecular junctions, namely gold/ trans-1,2-bis (4-pyridyl) ethylene/gold junction and gold/4,4'-bipyridine/gold junctions in various conditions were studied and the corresponding configurations were determined. The enhancement in SERS was also studied by employing the time-dependent density functional theory. Furthermore, we studied some properties of the interface, such as the stability of the adsorbates and charge transfer properties of molecular junctions. The decrease in the stability of molecules was found when adsorbed on metallic surface and trapped in metallic junctions. Our studies explained several puzzles and by rational design, more stable molecular devices were obtained.

Place, publisher, year, edition, pages
Stockholm, Sweden: KTH Royal Institute of Technology, 2016. 71 p.
TRITA-BIO-Report, ISSN 1654-2312 ; 2016:12
SERS, IETS, Interface, Chemical Stability
National Category
Natural Sciences Chemical Sciences Theoretical Chemistry
Research subject
Theoretical Chemistry and Biology
urn:nbn:se:kth:diva-185947 (URN)978-91-7595-992-4 (ISBN)
Public defence
2016-05-25, FA32, Roslagstullsbacken 21, Stockholm, 10:00 (English)
Available from: 2016-04-29 Created: 2016-04-29 Last updated: 2016-04-29Bibliographically approved

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Duan, SaiHu, WeiLuo, Yi
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