Electronic structure methods for studying surface-enhanced Raman scattering

Jensen, Lasse; Aikens, Christine M.; Schatz, George C.

doi:10.1039/b706023h

Cited by 613 publications

(636 citation statements)

References 142 publications

(190 reference statements)

Supporting

Mentioning

625

Contrasting

Unclassified

Order By: Relevance

“…As Jensen et al [22] suggested, the enhancement factor under off-resonance excitation is a measure of CHEM enhancement, which is due to ground state chemical interactions between the molecule and active substrate. Unlike the charge transfer enhancement, CHEM enhancement is not limited to the resonant or offresonant region because it is not associated with any excitations of the substrate-molecule system.…”

Section: Resultsmentioning

confidence: 99%

Direct measurement of the Raman enhancement factor of rhodamine 6G on graphene under resonant excitation

Deng

Wang

et al. 2014

Nano Res.

View full text Add to dashboard Cite

Graphene substrates have recently been found to generate Raman enhancement. Systematic studies using different Raman probes have been implemented, but one of the most commonly used Raman probes, rhodamine 6G (R6G), has yielded controversial results for the enhancement effect on graphene. Indeed, the Raman enhancement factor of R6G induced by graphene has never been measured directly under resonant excitation because of the presence of intense fluorescence backgrounds. In this study, a polarization-difference technique is used to suppress the fluorescence background by subtracting two spectra collected using different excitation laser polarizations. As a result, enhancement factors are obtained ranging between 1.7 and 5.6 for the four Raman modes of R6G at 611, 1,183, 1,361, and 1,647 cm -1 under resonant excitation by a 514.5 nm laser. By comparing these results with the results obtained under non-resonant excitation (632.8 nm) and pre-resonant excitation (593 nm), the enhancement can be attributed to static chemical enhancement (CHEM) and tuning of the molecular resonance. Density functional theory simulations reveal that the orbital energies and densities for R6G are modified by graphene dots.

show abstract

Section: Resultsmentioning

confidence: 99%

Direct measurement of the Raman enhancement factor of rhodamine 6G on graphene under resonant excitation

Deng

Wang

et al. 2014

Nano Res.

View full text Add to dashboard Cite

show abstract

“…The Becke-Perdew (BP86) XC-potential [91,92] and a triple-polarized slater type (TZP) basis set from the ADF basis set library were used in our simulation. The validity of using DFT and ADF for quantum mechanical SERS calculation has already been proven by many researchers [37][38][39][40][41][42][43][44][45][46][47][48].…”

Section: Computational Approach and Detailsmentioning

confidence: 98%

“…In this context, it is increasingly important to understand the microscopic nature of SERS using first principle modeling [43]. It is now widely believed that the chemical bonding effects in SERS can be simulated just by considering the local environment of a molecule which is also consistent with the adatom model [26,44].…”

mentioning

confidence: 99%

Metal−Molecule Schottky Junction Effects in Surface Enhanced Raman Scattering

2010

View full text Add to dashboard Cite

We propose a complementary interpretation of the mechanism responsible for the strong enhancement observed in Surface Enhanced Raman Scattering (SERS). The effect of a strong static local electric field due to Schottky barrier at the metal-molecule junction on SERS is systematically investigated. The study provides a viable explanation to the low repeatability of SERS experiments as well as the Raman peak shifts as observed in SERS and raw Raman spectra. It was found that strong electrostatic build-in field at the metal-molecule junction along specific orientations can result in 2-4 more orders of enhancement in SERS.

show abstract

“…Metal surfaces largely enhance (spontaneous) Raman spectra via the increased fields which exist in the vicinity of a surface plasmon excitation, [29][30][31] although there is also a chemical effect [32][33][34][35] which arises from the metal perturbing the electronic structure of an attached molecule. Classical electrodynamics can account for the former, 36 and TDDFT calculations can be used to describe the latter.…”

Section: Surface Effectsmentioning

confidence: 99%

Modeling Coherent Anti-Stokes Raman Scattering with Time-Dependent Density Functional Theory: Vacuum and Surface Enhancement.

Parkhill

Rappoport

Aspuru‐Guzik

2011

J. Phys. Chem. Lett.

View full text Add to dashboard Cite

We present the first density functional simulations of coherent anti-Stokes Raman scattering (CARS) and an analysis of the chemical effects upon binding to a metal surface. Spectra are obtained from first-principles electronic structure calculations and are compared with available experiments and previously available theoretical results following from Hartree–Fock polarizability derivatives. A first approximation to the nonresonant portion of the CARS signal is also explored. We examine the silver pyridine cluster models of the surface chemical signal enhancement, previously introduced for surface-enhanced Raman scattering. Chemical resonant intensity enhancements of roughly 102 are found for several model clusters. The prospects of realizing further enhancement of CARS signal with metal surfaces is discussed in light of the predicted chemical enhancements.

show abstract

Electronic structure methods for studying surface-enhanced Raman scattering

Cited by 613 publications

References 142 publications

Direct measurement of the Raman enhancement factor of rhodamine 6G on graphene under resonant excitation

Direct measurement of the Raman enhancement factor of rhodamine 6G on graphene under resonant excitation

Metal−Molecule Schottky Junction Effects in Surface Enhanced Raman Scattering

Modeling Coherent Anti-Stokes Raman Scattering with Time-Dependent Density Functional Theory: Vacuum and Surface Enhancement.

Contact Info

Product

Resources

About