New insights into the 1D carbon chain through the RPA.

Abstract

We investigated the electronic and structural properties of the infinite linear carbon chain (carbyne) using density functional theory (DFT) and the random phase approximation (RPA) to the correlation energy. The studies are performed in vacuo and for carbyne inside a carbon nano tube (CNT). In the vacuum, semi-local DFT and RPA predict bond length alternations of about 0.04 Å and 0.13 Å, respectively. The frequency of the highest optical mode at the Γ point is 1219 cm-1 and about 2000 cm-1 for DFT and the RPA. Agreement of the RPA to previous high level quantum chemistry and diffusion Monte-Carlo results is excellent. For the RPA we calculate the phonon-dispersion in the full Brillouine zone and find marked quantitative differences to DFT calculations not only at the Γ point but also throughout the entire Brillouine zone. To model carbyne inside a carbon nanotube, we considered a (10,0) CNT. Here the DFT calculations are even qualitatively sensitive to the k-points sampling. At the limes of a very dense k-points sampling, semi-local DFT predicts no bond length alternation (BLA), whereas in the RPA a sizeable BLA of 0.09 Å prevails. The reduced BLA leads to a significant red shift of the vibrational frequencies of about 350 cm-1, so that they are in good agreement with experimental estimates. Overall, the good agreement between the RPA and previously reported results from correlated wavefunction methods and experimental Raman data suggests that the RPA provides reliable results at moderate computational costs. It hence presents a useful addition to the repertoire of correlated wavefunction methods and its accuracy clearly prevails for low dimensional systems, where semi-local density functionals struggle to yield even qualitatively correct results.