Raman and IR spectra of graphdiyne nanoribbons

TL;DR

This study uses DFT calculations to analyze how lateral confinement influences the electronic, Raman, and IR spectra of { extgamma}-graphdiyne nanoribbons, providing insights into their vibrational properties and edge effects.

Contribution

It offers a detailed symmetry-based assignment of vibrational spectra and demonstrates the modulation of electronic and vibrational properties with nanoribbon width and edge structure.

Findings

Confinement affects vibrational modes and spectra.

Spectroscopic markers identify edge structures.

Band gap varies with nanoribbon width.

Abstract

{\gamma}-graphdiyne is a 2D carbon structure beyond graphene: it is formed by sp and sp2 carbon atoms organized as hexagonal rings connected by linear links, and it is predicted to be a semiconductor. The lateral confinement of {\gamma}-graphdiyne nanoribbons significantly affects the electronic and vibrational properties. By means of periodic Density Functional Theory (DFT) calculations we investigate here the electronic band structure, the Raman and IR spectra of the {\gamma}-graphdiyne 2D crystal and related nanoribbons. We discuss the effect of the functional and basis set on the evaluation of the band gap, highlighting the reliability of hybrid functionals. By joining DFT calculations with a symmetry analysis, we assign in detail the IR and Raman spectra of {\gamma}-graphdiyne. On this basis we show the modulation of the gap in nanoribbons of increasing width and different edges (armchair, zigzag). We assess how confinement affects the Raman and IR spectra of such nanoribbons by comparing their vibrational modes with the phonons of the parent 2D crystal. Our symmetry-based classification allows identifying the marker bands sensitive to the edge structure and lateral confinement of nanoribbons of increasing width. These results show the effectiveness of vibrational spectroscopy for the characterization of such nanostructures.