Polaron excitations in fullerenes: Theory as pi-conjugated systems

TL;DR

This paper reviews the theoretical modeling of polaronic excitations in fullerenes, focusing on electron-phonon interactions, lattice distortions, and optical properties, with results aligning well with experimental observations.

Contribution

It applies a Su-Schrieffer-Heeger type model to fullerenes, revealing polaron formation, energy level intrusions, and optical effects, advancing understanding of their electronic and vibrational properties.

Findings

Polaron formation causes energy level intrusions in doped fullerenes.

Optical spectra show new peaks due to polaronic distortions.

Theoretical results agree with experimental optical data.

Abstract

We review the recent theoretical treatment of fullerenes as pi-conjugated systems. Polaronic properties due to the Jahn-Teller type effects are mainly discussed. (1) A Su-Schrieffer-Heeger type electron-phonon model is applied to fullerenes: C_60 and C_70, and is solved with the adiabatic approximation to phonons. When the system (C_60 or C_70) is doped with one or two electrons (or holes), the additional charges accumulate along almost an equatorial line of the molecule. The dimerization becomes the weakest along the same line. Two energy levels, the occupied state and the empty state, intrude largely in the gap. The intrusion is larger in C_70 than in C_60. These are ``polarons'' in doped fullerenes. It is also found that C_60 and C_70 are related mutually with respect to electronical structures as well as lattice geometries. (2) We apply the model to the fullerene epoxide C_60O. It has the polaron-type lattice distortion around the oxygen, and also shows the energy level intrusion in the gap. (3) Optical properties of C_60 are calculated and discussed. In the absorption of the doped molecule, a new peak structure is present owing to the polaronic distortion. In the luminescence of the neutral C_60, the spacing between H_g(8)-phonon side-band peaks and the relative intensities agree well with experiments. In the dispersion of the third harmonic generation, the magnitudes of |chi^(3)| agree with those of experiments at the resonance of the lowest allowed transition as well as in the region away from the resonance.