Ultrafast Solvation Dynamics at Silica/Liquid Interfaces Probed by Time-Resolved Second Harmonic Generation

Shang, Xiaoming; Benderskii, and Alexander V.; Eisenthal, Kenneth B.

doi:10.1021/jp0105746

Cited by 41 publications

(50 citation statements)

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“…7 Many important reactions and fundamental processes take place at interfaces, membranes, and restricted environments, where the properties of the solvents change in a drastic manner. Numerous studies [14][15][16][17][18] show that the structure of water at interfaces is different from its structure in the bulk, and depends strongly on properties of the interfaces. An "icelike" structure was invoked for both hydrophobic 16 and hydrophilic 14,15 surfaces, but recent investigations using surface vibrational sum frequency spectroscopy indicate a rather liquidlike character.…”

Section: Introductionmentioning

confidence: 99%

“…Still, faster dynamics, as compared to the bulk, were also reported for the IR144 dye at the surface of SiO 2 particles in two different solvents, using time-resolved second harmonic generation. 14,15,33 In this contribution, we apply the same basic idea as in refs 29-31, namely, to use dyes, attached to the surface of ZrO 2 nanoparticles, as probes of the ultrafast solvation dynamics of the interfacial water. But here, we extend the range of techniques to probe the interface, by performing transient absorption and photon echo experiments, in addition to fluorescence upconversion.…”

Section: Introductionmentioning

confidence: 99%

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Aqueous Solvation Dynamics at Metal Oxide Surfaces

et al. 2006

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Broadband transient absorption (TA) spectroscopy, three-pulse photon echo peak shift (3PEPS), and anisotropy decay measurements were used to study the solvation dynamics in bulk water and interfacial water at ZrO 2 surfaces, using Eosin Y as a probe. The 3PEPS results show a multiexponential behavior with two subpicosecond components that are similar in bulk and interfacial water, while a third component of several picoseconds is significantly lengthened at the interface. The bandwidth correlation function from TA spectra exhibits the same behavior, and the TA spectra are well reproduced using the doorway-window picture with the time constants from PEPS. Our results suggest that interfacial water is restricted to a thickness of less than 5 Å. Also the high-frequency collective dynamics of water does not seem to be affected by the interface. On the other hand, the increase of the third component may point to a slowing down of diffusional motion at the interface, although other effects, may play a role, which are discussed.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Aqueous Solvation Dynamics at Metal Oxide Surfaces

et al. 2006

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“…For the study of surface phenomena at various interfaces, the total internal reflection (TIR) condition has been used in a number of spectroscopic measurements, 1 such as fluorometry, [2][3][4][5][6][7][8][9] surface enhanced infrared spectroscopy (SEIRA), [10][11][12] second harmonic generation, [13][14][15][16][17][18][19][20][21] and sum frequency generation (SFG). [22][23][24][25] There are two advantages when one uses the TIR condition.…”

Section: Introductionmentioning

confidence: 99%

Total-internal-reflection Broad-bandwidth Sum Frequency Generation Spectroscopy of Hexadecanethiol Adsorbed on Thin Gold Film Deposited on CaF, 2

et al. 2003

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IntroductionFor the study of surface phenomena at various interfaces, the total internal reflection (TIR) condition has been used in a number of spectroscopic measurements, 1 such as fluorometry, 2-9 surface enhanced infrared spectroscopy (SEIRA), [10][11][12] second harmonic generation, [13][14][15][16][17][18][19][20][21] and sum frequency generation (SFG). [22][23][24][25] There are two advantages when one uses the TIR condition. First, both incident light to the interface and reflected light or generated light from the interface travel in only one of the two phases adjacent to the interface, which circumvents bulk absorption by the other phase. One corollary is the freedom of changing the composition of the adjacent phase that has a lower refractive index. Second, high sensitivity to the interfaces can be achieved owing to the enhancement of the electric field at the interfaces. 1 The TIR arrangement can be employed at metal interfaces if a very thin metal film is used to avoid the absorption of light. It has been successfully employed to detect adsorbed species on metal in the SEIRA, where the thickness of the metal film is about 10 nm on a transparent substrate. [10][11][12] Recently, Williams et al. showed that the TIR arrangement can also be employed to detect SFG signals from alkanethiols adsorbed on a thin gold film. 24 However, detailed analysis of the sum frequency vibrational spectra has not been reported. SFG in the TIR arrangement has some potential as a powerful tool to study molecular orientations at metal/liquid interfaces, such as electrochemical interfaces, because it is free from bulk absorption and has interfacial sensitivity in the order of nanometers. Unlike surface plasmon resonance and capacitance measurements that have been used as sensitive means of detecting adsorption and molecular interaction at the interfaces, TIR-SFG will enable us to obtain molecular information on the solution side of the interfaces. One drawback of the TIR arrangement is the roughness of the metal surfaces. The roughness is prerequisite for high sensitivity and can complicate the interpretation of the experimental data because of the orientational distribution of molecules in comparison with those adsorbed on a single crystal surface. It is therefore of crucial importance to assess the degree of the variation in orientation of molecules.By using broad-bandwidth sum frequency generation (BBSFG) [26][27][28] we recently analyzed the orientation of alkanethiols adsorbed on Au(111). 29It is worthwhile to examine the applicability of BBSFG in the TIR condition at metal interfaces to obtain SFG spectra with higher resolution. In the present paper, we report the results of TIR-BBSFG measurements for hexadecanethiol (HDT) adsorbed on a thin gold film on CaF2. We will show that BBSFG can be successfully employed in the orientation analysis of the HDT molecules and that the methyl groups of HDT are much more randomly orientated than those on Au(111) on mica. Experimental SubstrateA hemicylindrical CaF2 prism (Pier Optic...

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“…IR144 has been frequently used in the development of nonlinear spectroscopic methods that probe the ultrafast solvation dynamics in liquids and on surfaces. [5][6][7][8][9][10] Until now most of studies on IR144 were performed in non-aqueous solution, 11,12 while its photophysical properties in aqueous solution are rarely reported, 13 which has limited its application in the near-infrared biomedical imaging as compared to IR125.…”

Section: Introductionmentioning

confidence: 99%

Aggregation Behaviors of Tricarbocyanine Dye in Water and in AOT Reverse Micelles

Zhu¹,

Ruixue²,

Lu³

et al. 2011

Chin. J. Chem.

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The photophysical property of the tricarbocyanine dye IR144 has been extensively studied in non-aqueous solvents. However, as a potential near-infrared biomedical imaging probe, the photophysical property of IR144 in water is still little known. So, the aggregation behaviors of IR144 in water with steady-state absorption spectroscopy and integrated polarization dependent femtosecond pump-probe spectroscopy were investigated. Through comparing the absorption spectral bandshape of IR144 in water and in water pool of AOT reverse micelles, It is found that IR144 form dimer aggregates in water even at very low concentration (＜1.0×10 -7 mol•L -1 ). And the absorption spectrum of the IR144 aggregates always displays a bimodal feature, which is independent of the dye concentration ranging from 1.0×10 -7 to 1.0×10 -4 mol•L -1 . For better understanding the aggregation behaviors of IR144 in water, we measured the ground state recovery kinetics and the reorientation kinetics of IR144 in water and in water pool of AOT reverse micelles (W 0 ＝[H 2 O]/[AOT], W 0 ＝40). It is found that the fluorescence quantum yield of IR144 in water is lower than that in water pool of AOT reverse micelles, and the reorientation time of IR144 in water is slower than that in water pool of AOT reverse micelles. Those kinetic measurements also verify that IR144 exists as dimer aggregates in water.

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Ultrafast Solvation Dynamics at Silica/Liquid Interfaces Probed by Time-Resolved Second Harmonic Generation

Cited by 41 publications

References 50 publications

Aqueous Solvation Dynamics at Metal Oxide Surfaces

Aqueous Solvation Dynamics at Metal Oxide Surfaces

Total-internal-reflection Broad-bandwidth Sum Frequency Generation Spectroscopy of Hexadecanethiol Adsorbed on Thin Gold Film Deposited on CaF, 2

Aggregation Behaviors of Tricarbocyanine Dye in Water and in AOT Reverse Micelles

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