Explanation of Surface-Enhanced Raman Scattering Intensities of <i>p</i>-Aminobenzenethiol by Density Functional Computations

Novak, V. R.; Dendisová, Marcela; Matějka, Pavel; Bouř, Petr

doi:10.1021/acs.jpcc.6b05947

Cited by 13 publications

(7 citation statements)

References 45 publications

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“…The general agreement between our derived molecular orientations and prior works that utilized specialized approaches that are uniquely sensitive to molecular orientation is remarkable given that our molecular models (isolated molecules in the gas phase) do not account for (i) intermolecular interactions on the surface, (ii) the modified polarizability and bonding of sulfur upon chemisorption, and (iii) the modified charge and protonation states that affect the resonance conditions in Raman spectroscopy . These obvious shortcomings, however, can be overcome by exploring different model molecular–metallic systems in the AIMD scheme.…”

Section: Resultsmentioning

confidence: 51%

Gauging Molecular Orientation through Time Domain Simulations of Surface-Enhanced Raman Scattering

2019

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Molecular reorientation dynamics modulate the physical and chemical properties of molecules at interfaces. This is particularly the case for organic molecules interacting with metallic surfacesstructural motifs of current interest to ultrasensitive chemical/biological detection/imaging. In this context, surface-enhanced Raman scattering (SERS) can be used to gauge the orientation of molecules in the immediate vicinity of plasmonic metals. Herein, we analyze SERS spectra of two aromatic thiols (4-mercaptobenzonitrile and thiophenol) chemisorbed onto silver substrates using ab initio molecular dynamics-based Raman spectral simulations that account for the optical response of molecules in the bulk and oriented molecules at the surface. Through a comparison with prior works aimed at gauging the orientation of our two model systems on metallic substrates, we describe the advantages and discuss the limitations of our described models and approach to gauging the orientation of molecules on metals through time domain simulations of their SERS signatures.

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Section: Resultsmentioning

confidence: 51%

Gauging Molecular Orientation through Time Domain Simulations of Surface-Enhanced Raman Scattering

2019

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“…Furthermore, on the basis of the model membranes with insertion of voltage-sensitive p -aminothiophenol (PATP) molecules (Figure S7), it was found that the conformational changes of the inserted PATP caused by light irradiation were identical to those from the direct application of external potentials (Figure C). The intensity of ν(C–C) at 1590 cm –1 of PATP was approximately linear with the increment of applied potential (Figure D). According to such linearity, the potential change induced by light irradiation could be calculated from the ν(C–C) peak intensity of the light-induced difference spectrum of the inserted PATP (dark line in Figure C); the resulting potential change is ∼0.05 V and is consistent with the measured transient potential drop (inset of Figure D, with a 808 nm, 0.3 W/cm 2 laser).…”

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confidence: 82%

Molecular Nature of Structured Water in the Light-Induced Interfacial Capacitance Changes at the Bioelectric Interface

Zhen

et al. 2021

J. Phys. Chem. Lett.

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Uncovering the function of structured water in the interfacial capacitance at the molecular level is the basis for the development of the concept and model of the electric double layer; however, the limitation of the available technology makes this task difficult. Herein, using surface-enhanced infrared absorption spectroscopy combined with electrochemistry, we revealed the contribution of the cleavage of loosely bonded tetrahedral water to the enhancement of model membrane capacitance. Upon further combination with ionic perturbation, we found that the interface hydrogen bonding environment in the stern layer was greatly significant for the light-induced cleavage of tetrahedral water and thus the conversion of optical signals into electrical signals. Our work has taken an important step toward gaining experimental insight into the relationship between water structure and capacitance at the bioelectric interface.

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“…One of the substances that seems destined to raise a seemingly never-ending set of questions about its behavior on plasmonic surfaces is 4-aminobenzenethiol (4-ABT). ,− Spectral bands of 4-ABT often observed in the SERS spectra could not be assigned to this molecule based on the knowledge of its normal Raman spectra . The origin of these bands was initially attributed to the enormous action of the charge transfer (CT) mechanism .…”

Section: Introductionmentioning

confidence: 99%

Laser-Induced Reactions of 4-Aminobenzenthiol Species Adsorbed on Ag, Au, and Cu Plasmonic Structures Followed by SERS Spectroscopy. The Role of Substrate and Excitation Energy – Surface-Complex Photochemistry and Plasmonic Catalysis

Kopal,

Švecová,

Jeřábek

et al. 2024

ACS Omega

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This study focuses on investigating the laser-induced reactions of various surface complexes of 4-aminobenzenethiol on Ag, Au, and Cu surfaces. By utilizing different excitation wavelengths, the distinct behavior of the molecule species on the plasmonic substrates was observed. Density functional theory (DFT) calculations were employed to establish the significant role of chemical enhancement mechanisms in determining the observed behavior. The interaction between 4-aminobenzenethiol (4-ABT) molecules and plasmonic surfaces led to the formation of surface complexes with absorption bands red-shifted into the visible and near-infrared regions. Photochemical transformations were induced by excitation wavelengths from these regions, with the nature of the transformations varying based on the excitation wavelength and the plasmonic metal. Resonance with the electronic absorption transitions of these complexes amplifies surface-enhanced Raman scattering (SERS), enabling the detailed examination of ongoing processes. A kinetic study on the Ag surface revealed processes governed by both first-and second-order kinetics, attributed to the dimerization process and transformation processes of individual molecules interacting with photons or plasmons. The behavior of the molecules was found to be primarily determined by the position and variability of the band between 1170 and 1190 cm −1 , with the former corresponding to molecules in the monomer state and the latter to dimerized molecules. Notably, laser-induced dimerization occurred most rapidly on the Cu surface, followed by Ag, and least on Au. These findings highlight the influence of plasmonic surfaces on molecular behavior and provide insights into the potential applications of laser-induced reactions for surface analysis and manipulation.

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Explanation of Surface-Enhanced Raman Scattering Intensities of p-Aminobenzenethiol by Density Functional Computations

Cited by 13 publications

References 45 publications

Gauging Molecular Orientation through Time Domain Simulations of Surface-Enhanced Raman Scattering

Gauging Molecular Orientation through Time Domain Simulations of Surface-Enhanced Raman Scattering

Molecular Nature of Structured Water in the Light-Induced Interfacial Capacitance Changes at the Bioelectric Interface

Laser-Induced Reactions of 4-Aminobenzenthiol Species Adsorbed on Ag, Au, and Cu Plasmonic Structures Followed by SERS Spectroscopy. The Role of Substrate and Excitation Energy – Surface-Complex Photochemistry and Plasmonic Catalysis

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