Microsolvation Effects on the Optical Properties of Crystal Violet

Loison, Claire; Antoine, Rodolphe; Broyer, M.; Dugourd, Philippe; Guthmuller, Julien; Simon, D.

doi:10.1002/chem.200800547

Cited by 28 publications

(28 citation statements)

References 45 publications

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“…We find that the image field effects are comparable to those due to solvation and are in good agreement with the experimental absorption spectra in solution where the two states are found at 587 and 539 nm, respectively. 48 We also find that the excitation energies depend strongly on the orientation of the molecule near the metal surface. Orientations where the transition dipole moment is aligned with the edge of the nanoparticle lead to shifts of up to 15 nm.…”

Section: Moleculeàmetal Interactions Within the Dim/qm Methodsmentioning

confidence: 95%

A Hybrid Atomistic Electrodynamics–Quantum Mechanical Approach for Simulating Surface-Enhanced Raman Scattering

et al. 2013

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Surface-enhanced Raman scattering (SERS) is a technique that has broad implications for biological and chemical sensing applications by providing the ability to simultaneously detect and identify a single molecule. The Raman scattering of molecules adsorbed on metal nanoparticles can be enhanced by many orders of magnitude. These enhancements stem from a twofold mechanism: an electromagnetic mechanism (EM), which is due to the enhanced local field near the metal surface, and a chemical mechanism (CM), which is due to the adsorbate specific interactions between the metal surface and the molecules. The local field near the metal surface can be significantly enhanced due to the plasmon excitation, and therefore chemists generally accept that the EM provides the majority of the enhancements. While classical electrodynamics simulations can accurately simulate the local electric field around metal nanoparticles, they offer few insights into the spectral changes that occur in SERS. First-principles simulations can directly predict the Raman spectrum but are limited to small metal clusters and therefore are often used for understanding the CM. Thus, there is a need for developing new methods that bridge the electrodynamics simulations of the metal nanoparticle and the first-principles simulations of the molecule to facilitate direct simulations of SERS spectra. In this Account, we discuss our recent work on developing a hybrid atomistic electrodynamics-quantum mechanical approach to simulate SERS. This hybrid method is called the discrete interaction model/quantum mechanics (DIM/QM) method and consists of an atomistic electrodynamics model of the metal nanoparticle and a time-dependent density functional theory (TDDFT) description of the molecule. In contrast to most previous work, the DIM/QM method enables us to retain a detailed atomistic structure of the nanoparticle and provides a natural bridge between the electronic structure methods and the macroscopic electrodynamics description. Using the DIM/QM method, we have examined in detail the importance of the local environment on molecular excitation energies, enhanced molecular absorption, and SERS. Our results show that the molecular properties are strongly dependent not only on the distance of the molecule from the metal nanoparticle but also on its orientation relative to the nanoparticle and the specific local environment. Using DIM/QM to simulate SERS, we show that there is a significant dependence on the adsorption site. Furthermore, we present a detailed comparison between enhancements obtained from DIM/QM simulations and those from classical electrodynamics simulations of the local field. While we find qualitative agreement, there are significant differences due to the neglect of specific molecule-metal interactions in the classical electrodynamics simulations. Our results highlight the importance of explicitly considering the specific local environment in simulations of molecule-plasmon coupling.

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Section: Moleculeàmetal Interactions Within the Dim/qm Methodsmentioning

confidence: 95%

A Hybrid Atomistic Electrodynamics–Quantum Mechanical Approach for Simulating Surface-Enhanced Raman Scattering

et al. 2013

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“…These UV-VIS results for [RA] 2support the previous hypothesis of solvent specific interaction used to justify the presence of the higher-energy shoulder observed in CV absorption spectrum. 14,26 Aiming to better support such assumptions, a resonance Raman investigation was done.…”

Section: Resultsmentioning

confidence: 99%

“…In the same paper Kahr et al showed that Raman spectroscopy was unable to distinguish between to CV hydrates in different crystalline symmetry groups. 22 More recently Loison et al 26 showed that the shoulder is due to interactions of CV with its environment, by presenting the photodissociation spectra for isolated CV and CV-H 2 O complex without and with a shoulder, respectively.…”

Section: Introductionmentioning

confidence: 99%

Unraveling the Solvatochromism of a Triarylmethane Dye by Resonance Raman Spectroscopy

Monezi¹,

Lepre²,

Ando³

2019

Quím. Nova

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Recebido em 26/06/2019; aceito em 04/09/2019; publicado na web em 21/10/2019 The effect of the solvent on the electronic properties of the triarylmethane dye rosolic acid (RA) is investigated by means of UV-VIS and resonance Raman (RR) spectroscopies. The comparison of the solvatochromic behavior of both neutral and dianionic species of RA in acetonitrile, dimethylsulfoxide, and methanol illustrates the effect of polarity and hydrogen bonding on their electronic transitions. The resonance Raman analysis revealed two distinct chromophores in both neutral and dianionic species: i) one located at the central carbon atom, acting as an electron acceptor, and ii) the other involving the π-system of the donor groups. The observed resonance Raman excitation profiles are solvent dependent and could be interpreted as the effect of the solvent on the planarity of the aromatic rings in relation to the central carbon atom. In the case of neutral RA species, having C 2 symmetry, specific hydrogen bonding interactions are responsible for inducing a symmetry increase. The opposite effect was observed for the dianionic species [RA] 2-, having D 3 propeller symmetry, where the interactions with the solvent induces a lowering of the symmetry.

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“…This is consistent with previous gas phase measurements of rhodamine derivatives, where similar profiles to those observed in solution are also found, and indeed with other poly-aromatic dyes, indicating this may be a more general phenomenon. 20,22,23,35,36 Additionally, gas-phase action spectroscopy performed upon pseudo-dimers of rhodamine 575, where the dimerization is created by enforced proximity of the dyes following grafting onto a tri-peptide, shows there is only a small shift in the position of the absorption maximum relative to the monomeric species. 31 Moreover, recent solution phase measurements of pyronin B dimers in solution found their absorption and fluorescence properties to differ only very slightly from the monomer.…”

Section: Resultsmentioning

confidence: 99%

The Gas-Phase Photophysics of Eosin Y and its Maleimide Conjugate

et al. 2016

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The use of the xanthene family of dyes as fluorescent probes in a wide range of applications has provided impetus for the studying of their photophysical properties. In particular, recent advances in gas-phase techniques such as FRET that utilize such chromophores have placed a greater importance on the characterization of these properties in the gas phase. Additionally, the use of synthetic linker chains to graft the chromophores in a site-specific manner to their target system is ubiquitous. There is, however, often limited information on how the addition of such a linker chain may affect the photophysical properties of the chromophores, which is of fundamental importance for interpretation of experimental data reliant on grafted chromophores. Here, we present data on the optical spectroscopy of different protonation states of Eosin Y, a fluorescein derivative. We compare the photophysics of Eosin Y to its maleimide conjugate, and to the thioether product of the reaction of this conjugate with cysteamine. Comparison of the mass spectra following laser irradiation shows that very different relaxation takes place upon addition of the maleimide moiety but that the photophysics of the bare chromophore are restored upon addition of cysteamine. This radical change in the photophysics is interpreted in terms of charge-transfer states, whose energy relative to the S1 ← S0 transition of the chromophore is dependent on the conjugation of the maleimide moiety. We also show that the shape of the absorption band is unchanged in the gas-phase as compared to the solution-phase, showing a maximum with a shoulder toward the blue, and examination of isotope distributions of the isolated ions show that this shoulder cannot be due to the presence of dimers. Consideration of the fluorescence emission spectrum allows a tentative assignment of the shoulder to be due to a vibrational progression with a high Franck-Condon factor.

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Microsolvation Effects on the Optical Properties of Crystal Violet

Cited by 28 publications

References 45 publications

A Hybrid Atomistic Electrodynamics–Quantum Mechanical Approach for Simulating Surface-Enhanced Raman Scattering

A Hybrid Atomistic Electrodynamics–Quantum Mechanical Approach for Simulating Surface-Enhanced Raman Scattering

Unraveling the Solvatochromism of a Triarylmethane Dye by Resonance Raman Spectroscopy

The Gas-Phase Photophysics of Eosin Y and its Maleimide Conjugate

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