Kohn anomalies and non-adiabaticity in doped carbon nanotubes

TL;DR

This study uses DFT and an analytical model to investigate how doping affects Kohn anomalies in metallic carbon nanotubes, revealing that non-adiabatic effects are crucial for accurate predictions of phonon behavior.

Contribution

It demonstrates that non-adiabatic effects significantly alter the predicted Kohn anomalies in doped carbon nanotubes, challenging previous adiabatic assumptions.

Findings

Kohn anomalies occur near band crossings when non-adiabatic effects are included.

Doping levels influence the appearance and linewidth of the G- peak in Raman spectra.

Non-adiabatic effects suppress certain anomalies predicted by the Born-Oppenheimer approximation.

Abstract

The high-frequency Raman-active phonon modes of metallic single-walled carbon nanotubes (SWNTs) are thought to be characterized by Kohn anomalies (KAs), which are expected to be modified by the doping-induced tuning of the Fermi energy level $\epsilon_F$, obtained through the intercalation of SWNTs with alkali atoms or by the application of a gate potential. We present a Density-Functional Theory (DFT) study of the phonon properties of a (9,9) metallic SWNT as a function of electronic doping. For such study, we use, as in standard DFT calculations of vibrational properties, the Born-Oppenheimer (BO) approximation. We also develop an analytical model capable of reproducing and interpreting our DFT results. Both DFT calculations and this model predict, for increasing doping levels, a series of EPC-induced KAs in the vibrational mode parallel to the tube axis at the $\mathbf\Gamma$ point of the Brillouin zone, usually indicated in Raman spectroscopy as the $G^-$ peak. Such KAs would arise each time a new conduction band is populated. However, we show that they are an artifact of the BO approximation. The inclusion of non-adiabatic (NA) effects dramatically affects the results, predicting KAs at $\mathbf\Gamma$ only when $\epsilon_F$ is close to a band crossing $E_{X}$. For each band crossing a double KA occurs for $\epsilon_F=E_{X}\pm \hbar\omega/2$, where $\hbar\omega$ is the phonon energy. In particular, for a 1.2 $nm$ metallic nanotube, we predict a KA to occur in the so-called $G^-$ peak at a doping level of about $N_{el}/C=\pm 0.0015$ atom ($\epsilon_F\approx \pm 0.1 ~eV$). Furthermore, we predict that the Raman linewidth of the $G^-$ peak significantly decreases for $|\epsilon_F| \geq \hbar\omega/2$.