Infrared-active phonons in one-dimensional materials and their spectroscopic signatures
Norma Rivano, Nicola Marzari, Thibault Sohier
Abstract
Abstract Dimensionality provides a clear fingerprint on the dispersion of infrared-active, polar-optical phonons. For these phonons, the local dipoles parametrized by the Born effective charges drive the LO-TO splitting of bulk materials; this splitting actually breaks down in two-dimensional materials. Here, we develop the theory for one-dimensional (1D) systems—nanowires, nanotubes, and atomic and polymeric chains. Combining an analytical model with the implementation of density-functional perturbation theory in 1D boundary conditions, we show that the dielectric splitting in the dispersion relations collapses as $${x}^{2}\log (x)$$ <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msup><mml:mrow><mml:mi>x</mml:mi></mml:mrow><mml:mrow><mml:mn>2</mml:mn></mml:mrow></mml:msup><mml:mi>log</mml:mi><mml:mrow><mml:mo>(</mml:mo><mml:mrow><mml:mi>x</mml:mi></mml:mrow><mml:mo>)</mml:mo></mml:mrow></mml:mrow></mml:math> at the zone center. The dielectric properties and the radius of the 1D materials are linked by the present work to these red shifts, opening infrared and Raman characterization avenues.