Experimental and theoretical study of infrared active phonons in heavily doped K x p -terphenyl

We present an experimental and theoretical study of the infrared-active phonon modes of heavily potassium (K) doped p -terphenyl, a material of great current interest due to reports of high-temperature superconductivity. First, we show that the phonon features in the fingerprint region of the midinfrared domain can be well reproduced through the density functional theory (DFT) quantum-chemical simulations. Compelling evidence for a distorted organic molecular framework is obtained here from the emergence of up to three absorption bands that are predicted to be infrared (IR)-inactive under idealized D 2 h planar symmetry and a systematic softening of specific vibrational modes. Computational models of twisted conformers exhibiting reduced D 2 or C 2 h symmetry are shown to successfully reproduce the activation of these silent modes and the redshifting shown by others. Second, we present an analysis of the lineshape of the experimental IR-phonon modes in a wide temperature range from 6 to 300 K. We show that several of the IR phonons have a strongly asymmetric shape that is indicative of a Fano-like interaction with the doped charge carriers. Notably, we find that the phonon asymmetries, and the corresponding Fano parameters, undergo anomalous changes around 100 K that are reminiscent of a charge localization transition around 90 K that has been previously reported from a corresponding study of the low-energy electronic response.