Visualization of Vibrational Modes in Real Space by Tip‐Enhanced Non‐Resonant Raman Spectroscopy

Duan, Sai; Tian, Guangjun; Luo, Yi

doi:10.1002/anie.201508218

Cited by 54 publications

(68 citation statements)

References 34 publications

(32 reference statements)

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“…Tip-enhanced Raman spectroscopy (TERS) is a powerful technique resulting in strongly increasing Raman signals from molecules attached to a metallic nanostructure. It is of great significance in many fields such as chemistry, biology, medicine, pharmacology, and environmental science [1][2][3][4][5][6][7][8][9][10][11][12][13][14]. TERS is one of the useful tools for detecting single molecule with high sensitivity and molecular specificity.…”

Section: Introductionmentioning

confidence: 99%

Selective Excitation on Tip-Enhanced Raman Spectroscopy by Pulse Shaping Femtosecond Laser

et al. 2018

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In this paper, we propose a scheme for achieving ultrafast coherent control of the selective excitation among three excited states in stimulated Raman scattering process on a tip-enhanced Raman spectroscopy (TERS). The center frequencies of the pump and Stokes laser pulses are 14,000 cm −1 and 12,500 cm −1 , and their spectral bandwidths are both 700 cm −1. By properly modulating the spectral phase distribution and cutting the frequency components, the stimulated Raman transition probabilities of two excited state keep maximal, while the other one can be suppressed to zero. The shaped pump and Stokes pulse irradiate obliquely into the TERS nanostructure containing a single layer molecule. The impulse response in temporal and frequency domain is calculated by using finite-difference time-domain (FDTD) simulation followed by Fourier transform. The frequency components and the relative phase are same with the corresponding input pulses, but the intensities are enhanced by more than 10 times. Compared with the case without the TERS nanostructure, the probability of selective excited Raman transition increases by more than 4 orders of magnitude, and the selective depressed Raman peak keeps at 0.

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Section: Introductionmentioning

confidence: 99%

Selective Excitation on Tip-Enhanced Raman Spectroscopy by Pulse Shaping Femtosecond Laser

et al. 2018

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“…As subnanometer resolution is difficult to understand in terms of the classical electromagnetic theory, these results have inspired theoreticians to work on proposing new mechanisms that could explain the results. Duan and Luo have proposed involvement of nonlinear optical processes [47]. Creation of an "atomic-scale hot spot" has also been proposed [48].…”

Section: Understanding Tersmentioning

confidence: 99%

Nanoscale Insights into Enhanced Raman Spectroscopy

Rzeznicka¹,

Horino²

2018

Raman Spectroscopy

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Enhanced Raman spectroscopies, such as surface-enhanced Raman spectroscopy (SERS) and tip-enhanced Raman spectroscopy (TERS), are based on the amplification of intrinsically weak Raman signals of a molecule by metallic nanostructures. The main enhancement is attributed to electromagnetic enhancement. Chemical effects, such as formation of a surface complex, or a charge-transfer complex, co-adsorbed anion effect, also add to the enhancement of the signal. Using SERS, it has been difficult to study details of chemical enhancement and polarization effects due to limited optical resolution of the technique and usage of roughened metal surfaces. These obstacles were overcome with the development of the TERS technique. TERS has extended Raman spectroscopy into the nanoscale region. In this chapter, nanoscale insights into surface chemistry that lead to Raman signal enhancement are described. The effect of molecular binding and orientation as well as commonly used in SERS chloride activation of metal surfaces is discussed. Finally, we describe the future prospects of TERS and the challenges that keep us from harnessing the full potential of the technique.

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“…To theoretically predict the Raman images, the localization of the plasmonic field has to be taken into account. In this context, the interaction Hamiltonian between adsorbates and plasmonic field could be written as 102,103…”

Section: Localization Of the Electromagnetic Fieldmentioning

confidence: 99%

Theoretical modeling of surface and tip‐enhanced Raman spectroscopies

Duan

Luo

2016

WIREs Comput Mol Sci

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Raman spectroscopy is a powerful technique in molecular science because of the ability of providing vibrational ‘finger‐print’. The developments of the surface‐enhanced Raman spectroscopy (SERS) and tip‐enhanced Raman spectroscopy (TERS) have significantly improved the detection sensitivity and efficiency. However, they also introduce complications for the spectral assignments, for which advanced theoretical modeling has played an important role. Here we summarize some of our recent progresses for SERS and TERS, which generally combine both solid‐state physics and quantum chemistry methods with two different schemes, namely the cluster model and the periodic boundary condition (PBC) model. In the cluster model, direct Raman spectra calculations are performed for the cluster taken from the accurate PBC structure. For PBC model, we have developed a quasi‐analytical approach that enables us to calculate the Raman spectra of entire system. Under the TERS condition, the non‐uniformity of plasmonic field in real space can drastically alter the interaction between the molecule and the light. By taking into account the local distributions of the plasmonic field, a new interaction Hamiltonian is constructed and applied to model the super‐high‐resolution Raman images of a single molecule. It shows that the resonant Raman images reflect the transition density between ground and excited states, which are generally vibrational insensitive. The nonresonant Raman images, on the other hand, allow to visualize the atomic movement of individual vibrational modes in real space. The inclusion of non‐uniformity of plasmonic field provides ample opportunities to discover new physics and new applications in the future. WIREs Comput Mol Sci 2017, 7:e1293. doi: 10.1002/wcms.1293 This article is categorized under: Structure and Mechanism > Molecular Structures Structure and Mechanism > Computational Materials Science Theoretical and Physical Chemistry > Spectroscopy

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Visualization of Vibrational Modes in Real Space by Tip‐Enhanced Non‐Resonant Raman Spectroscopy

Cited by 54 publications

References 34 publications

Selective Excitation on Tip-Enhanced Raman Spectroscopy by Pulse Shaping Femtosecond Laser

Selective Excitation on Tip-Enhanced Raman Spectroscopy by Pulse Shaping Femtosecond Laser

Nanoscale Insights into Enhanced Raman Spectroscopy

Theoretical modeling of surface and tip‐enhanced Raman spectroscopies

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