Dataset Information

First-Principles Simulations of Tip Enhanced Raman Scattering Reveal Active Role of Substrate on High-Resolution Images.

ABSTRACT: Tip-enhanced Raman scattering (TERS) has emerged as a powerful tool to obtain subnanometer spatial resolution fingerprints of atomic motion. Theoretical calculations that can simulate the Raman scattering process and provide an unambiguous interpretation of TERS images often rely on crude approximations of the local electric field. In this work, we present a novel and first-principles-based method to compute TERS images by combining Time Dependent Density Functional Theory (TD-DFT) and Density Functional Perturbation Theory (DFPT) to calculate Raman cross sections with realistic local fields. We present TERS results on free-standing benzene and C₆₀ molecules, and on the TCNE molecule adsorbed on Ag(100). We demonstrate that chemical effects on chemisorbed molecules, often ignored in TERS simulations of larger systems, dramatically change the TERS images. This observation calls for the inclusion of chemical effects for predictive theory-experiment comparisons and an understanding of molecular motion at the nanoscale.

SUBMITTER: Litman Y

PROVIDER: S-EPMC10405274 | biostudies-literature | 2023 Aug

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

First-Principles Simulations of Tip Enhanced Raman Scattering Reveal Active Role of Substrate on High-Resolution Images.

Litman Yair Y Bonafé Franco P FP Akkoush Alaa A Appel Heiko H Rossi Mariana M

The journal of physical chemistry letters 20230724 30

Tip-enhanced Raman scattering (TERS) has emerged as a powerful tool to obtain subnanometer spatial resolution fingerprints of atomic motion. Theoretical calculations that can simulate the Raman scattering process and provide an unambiguous interpretation of TERS images often rely on crude approximations of the local electric field. In this work, we present a novel and first-principles-based method to compute TERS images by combining Time Dependent Density Functional Theory (TD-DFT) and Density F ...[more]

PMID: 37487223

Similar Datasets

Project description:Tip-enhanced Raman spectroscopy (TERS) has recently been developed to push the spatial resolution down to single-chemical-bond scale. The morphology of the scanning tip, especially the atomistic protrusion at the tip apex, plays an essential role in obtaining both high spatial resolution and large field enhancement at the Ångström level. Although it is very difficult to directly characterize the atomistic structures of the tip, the Raman scattering from the apex's own vibrations of the metal tip can provide valuable information about the stacking of atoms at the tip apex. However, conventional quantum chemistry packages can only simulate the Raman scattering of small metal clusters with few atoms due to huge computational cost, which is not enough since the shaft of the tip behind the apex also makes significant contributions to the polarizabilities of the whole tip. Here we propose an atomistic polarization model to simulate the Raman spectra of large metal tips at subwavelength scales based on the combination of the atomistic discrete dipole approximation model and the density functional theory. The atomistic tip with different sizes and stacking structures is considered in its entirety during the calculation of polarizabilities, and only the vibrational contributions from the tip apex are taken into account to simulate the Raman spectra of the tip. The Raman spectral features are found to be very sensitive to the local constituent element at the tip apex, atomic stacking modes, and shape of the tip apex, which can thus be used as a fingerprint to identify different atomistic structures of the tip apex. Moreover, our approaches can be extended to the metal tips with sub-wavelength sizes, making it possible to consider both the large scale and the atomistic detail of the tip simultaneously. The method presented here can be used as a basic tool to simulate the Raman scattering process of the metal tips and other nanostructures in an economic way, which is beneficial for understanding the roles of atomistic structures in tip- and surface-enhanced spectroscopies.

Dataset Information

First-Principles Simulations of Tip Enhanced Raman Scattering Reveal Active Role of Substrate on High-Resolution Images.

Publications

First-Principles Simulations of Tip Enhanced Raman Scattering Reveal Active Role of Substrate on High-Resolution Images.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets