Resonance Raman and hyper‐Raman spectroscopy of organic chromophores for second‐order nonlinear optics

Kelley, Anne Myers

doi:10.1002/qua.20520

Cited by 18 publications

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References 69 publications

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“…The greatest attention has been focused on surface-enhanced Raman scattering ͑SERS͒. Despite the well understood relationship between optical absorption and resonance Raman scattering, [20][21][22][23][24][25] few studies have directly addressed the optical absorption spectra of molecules bound to SERSactive substrates, [26][27][28][29][30][31][32][33] in part because of experimental challenges in making such measurements. The electromagnetic enhancement model for SERS assumes that the properties of the adsorbed molecule are largely unchanged by its proximity to the metal.…”

Section: Introductionmentioning

confidence: 99%

A molecular spectroscopic view of surface plasmon enhanced resonance Raman scattering

Kelley

2008

The Journal of Chemical Physics

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The enhancement of resonance Raman scattering by coupling to the plasmon resonance of a metal nanoparticle is developed by treating the molecule-metal interaction as transition dipole coupling between the molecular electronic transition and the much stronger optical transition of the nanoparticle. A density matrix treatment accounts for coupling of both transitions to the electromagnetic field, near-resonant energy transfer between the molecule-excited and nanoparticle-excited states, and dephasing processes. This fully quantum mechanical approach reproduces the interference effects observed in extinction spectra of J-aggregated dyes adsorbed to metal nanoparticles and makes testable predictions for surface-enhanced resonance Raman excitation profiles.

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Section: Introductionmentioning

confidence: 99%

A molecular spectroscopic view of surface plasmon enhanced resonance Raman scattering

Kelley

2008

The Journal of Chemical Physics

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Ferrocenyl‐Ended Thieno–Vinylene Oligomers: Donor–Acceptor Polarization and Mixed‐Valence Properties with Emphasis on the Raman Mapping of Localized‐to‐Delocalized Transitions

Casado

González

Delgado

et al. 2009

Chemistry A European J

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What's your role? New oligothiophene-vinylene compounds have been synthesized to study the role of the conjugated chain in two different cases (see scheme; MV=mixed valence). The electronic and molecular structures were analyzed by means of electronic, X-ray photoelectron, and Raman spectroscopy, together with thermo spectroscopy, electrochemistry, and DFT calculations.New oligothiophene-vinylene compounds have been synthesized in order to study the role of the conjugated chain in two different cases: 1) when push-pull action operates between an electron-donor and an electron-acceptor group at the ends of the thiophene-vinylene conjugated chain, and 2) when mixed-valence action is induced by single oxidation of the same chain functionalized at both terminal positions with ferrocene groups leading to competition between the donor groups. The electronic and molecular structures are analyzed by means of electronic, X-ray photoelectron and Raman spectroscopies, together with thermospectroscopy, electrochemistry and density functional theory calculations. The cyclic voltammetry processes have been followed by spectrochemistry. It is shown that the radical cation of the diferrocenyl derivative is a class III mixed-valence system (i.e., fully delocalized) according to its Raman spectrum. Moreover, by Raman thermo-spectroscopy the thermal transition of this radical cation from a delocalized (class III, room temperature) to a localized (class II, -160 degrees C) state is scanned. In all cases the Raman study is paralleled by an electronic absorption spectroscopic analysis. Structure-property relationships are proposed for molecules of two important fields of very active research as that of the non-linear optics (i.e., organic optoelectronic) and that of the mixed-valence systems (i.e., charge-transfer processes).

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Surface‐enhanced resonance Raman and hyper‐Raman spectroscopy of water‐soluble substituted stilbene and distyrylbenzene chromophores

Leng¹,

Woo²,

Vak³

et al. 2006

J Raman Spectroscopy

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Surface-enhanced Raman spectra (SERS) are presented for two water-soluble, donor-donor-or donor-acceptor-substituted phenylene vinylene derivatives adsorbed on the surfaces of colloidal silver nanoparticles. The normally water-insoluble, substituted stilbene and distyrylbenzene chromophores have been modified by attaching trimethylammoniumalkyl chains to the amino donor group, creating both aqueous solubility and a net positive charge that facilitates binding to citrate-or borohydride-reduced silver colloids. A symmetrically donor-substituted distyrylbenzene exhibits strong electronically pre-resonant SERS spectra that are not highly dependent on excitation wavelength and are qualitatively similar to the solution-phase resonance Raman (RR) spectra. A donor-acceptor-substituted stilbene exhibits weaker SERS enhancement despite being fully electronically resonant. The spectra vary considerably with excitation wavelength and show new lines not present in the solution-phase spectra, which are attributed to a photoproduct formed on the surface. Two-photon resonant hyper-Raman spectra are also presented for the donor-acceptor stilbene, both with and without surface enhancement.

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Resonance Raman and hyper‐Raman spectroscopy of organic chromophores for second‐order nonlinear optics

Cited by 18 publications

References 69 publications

A molecular spectroscopic view of surface plasmon enhanced resonance Raman scattering

A molecular spectroscopic view of surface plasmon enhanced resonance Raman scattering

Ferrocenyl‐Ended Thieno–Vinylene Oligomers: Donor–Acceptor Polarization and Mixed‐Valence Properties with Emphasis on the Raman Mapping of Localized‐to‐Delocalized Transitions

Surface‐enhanced resonance Raman and hyper‐Raman spectroscopy of water‐soluble substituted stilbene and distyrylbenzene chromophores

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