Recent progress and frontiers in the electromagnetic mechanism of surface-enhanced Raman scattering

Yamamoto, Yuko S.; Ozaki, Yukihiro; Itoh, Tamitake

doi:10.1016/j.jphotochemrev.2014.10.001

Cited by 141 publications

(117 citation statements)

References 96 publications

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“…42 Concerning the vibrational spectroscopy, the mechanism of SERS has extensively been studied, in particular, in the field of molecular science with main focus on the mechanisms of surface enhancements. 35,43,44 However, corresponding theoretical studies for the infrared absorption have been scarce, in particular, studies focusing on the effects of spatial structures of near-fields, and theoretical tools still need to be developed. In this study, we propose a theoretical method for infrared absorption spectroscopy with near-field on the basis of the multipolar Hamiltonian.…”

Section: Introductionmentioning

confidence: 99%

Generalized theoretical method for the interaction between arbitrary nonuniform electric field and molecular vibrations: Toward near-field infrared spectroscopy and microscopy

Iwasa

Takenaka

Taketsugu

2016

The Journal of Chemical Physics

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A theoretical method to compute infrared absorption spectra when a molecule is interacting with an arbitrary nonuniform electric field such as near-fields is developed and numerically applied to simple model systems. The method is based on the multipolar Hamiltonian where the light-matter interaction is described by a spatial integral of the inner product of the molecular polarization and applied electric field. The computation scheme is developed under the harmonic approximation for the molecular vibrations and the framework of modern electronic structure calculations such as the density functional theory. Infrared reflection absorption and near-field infrared absorption are considered as model systems. The obtained IR spectra successfully reflect the spatial structure of the applied electric field and corresponding vibrational modes, demonstrating applicability of the present method to analyze modern nanovibrational spectroscopy using near-fields. The present method can use arbitral electric fields and thus can integrate two fields such as computational chemistry and electromagnetics. C 2016 AIP Publishing LLC. [http://dx

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Section: Introductionmentioning

confidence: 99%

Generalized theoretical method for the interaction between arbitrary nonuniform electric field and molecular vibrations: Toward near-field infrared spectroscopy and microscopy

Iwasa

Takenaka

Taketsugu

2016

The Journal of Chemical Physics

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“…Raman scattering involving individual optical centers is a well-established molecular process used as a spectroscopic [1][2][3] and microscopic tool 4,5 with an ever-increasing range of applications, including surface-enhanced spectroscopy, [6][7][8][9][10][11] sensing, [12][13][14] the detection of environmental pollutants, 15,16 and identification of disease. 17 The theoretical basis for the underlying phenomenon is well-known and established with quantum electrodynamical techniques offering a particularly insightful means of formulation.…”

Section: Introductionmentioning

confidence: 99%

Raman scattering mediated by neighboring molecules

Williams

Andrews

2016

The Journal of Chemical Physics

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Raman scattering is most commonly associated with a change in vibrational state within individual molecules, the corresponding frequency shift in the scattered light affording a key way of identifying material structures. In theories where both matter and light are treated quantum mechanically, the fundamental scattering process is represented as the concurrent annihilation of a photon from one radiation mode and creation of another in a different mode. Developing this quantum electrodynamical formulation, the focus of the present work is on the spectroscopic consequences of electrodynamic coupling between neighboring molecules or other kinds of optical center. To encompass these nanoscale interactions, through which the molecular states evolve under the dual influence of the input light and local fields, this work identifies and determines two major mechanisms for each of which different selection rules apply. The constituent optical centers are considered to be chemically different and held in a fixed orientation with respect to each other, either as two components of a larger molecule or a molecular assembly that can undergo free rotation in a fluid medium or as parts of a larger, solid material. The two centers are considered to be separated beyond wavefunction overlap but close enough together to fall within an optical near-field limit, which leads to high inverse power dependences on their local separation. In this investigation, individual centers undergo a Stokes transition, whilst each neighbor of a different species remains in its original electronic and vibrational state. Analogous principles are applicable for the anti-Stokes case. The analysis concludes by considering the experimental consequences of applying this spectroscopic interpretation to fluid media; explicitly, the selection rules and the impact of pressure on the radiant intensity of this process

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“…From the discovery of the SERS phenomenon, the observations have provided fruitful information on the optical response of matter in the LSPR field, such as characteristic absorption, emission, and electronic and vibrational excitations [6][7][8]. The established SERS model explains the apparent enhancement factor of the SERS signal by considering the intensity of the localized electromagnetic field.…”

Section: Introductionmentioning

confidence: 99%

Single-site surface-enhanced Raman scattering beyond spectroscopy

2016

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Recent progress in the observation of surface-enhanced Raman scattering (SERS) is reviewed to examine the possibility of finding a novel route for the effective photoexcitation of materials. The importance of well-controlled SERS experiments on a single molecule at a single site is discussed based on the difference in the information obtained from ensemble SERS measurements using multiple active sites with an uncontrolled number of molecules. A single-molecule SERS observation performed at a mechanically controllable breaking junction with a simultaneous conductivity measurement provides clear evidence of the drastic changes both in the intensity and in the Raman mode selectivity of the electromagnetic field generated by localized surface plasmon resonance. Careful control of the field at a few-nanometer-wide gap of a metal nanodimer results in the modification of the selection rule of electronic excitation of an isolated single-walled carbon nanotube. The examples shown in this review suggest that a single-site SERS observation could be used as a novel tool to find, develop, and implement applications of plasmon-induced photoexcitation of materials.

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Recent progress and frontiers in the electromagnetic mechanism of surface-enhanced Raman scattering

Cited by 141 publications

References 96 publications

Generalized theoretical method for the interaction between arbitrary nonuniform electric field and molecular vibrations: Toward near-field infrared spectroscopy and microscopy

Generalized theoretical method for the interaction between arbitrary nonuniform electric field and molecular vibrations: Toward near-field infrared spectroscopy and microscopy

Raman scattering mediated by neighboring molecules

Single-site surface-enhanced Raman scattering beyond spectroscopy

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