Charge-sensitive vibrational modes in BEDT-TTF salts: Signatures of charge ordering and site charge

TL;DR

This study investigates vibrational modes in BEDT-TTF salts to understand charge ordering and site charge, highlighting the limitations of using vibrational frequency shifts for precise charge determination.

Contribution

It analyzes the reliability of C=C stretching modes in BEDT-TTF salts for detecting charge order and quantifying site charge, revealing significant uncertainties.

Findings

Frequency shifts of vibrational modes correlate with charge but have large variability.

Charge distribution estimates have an uncertainty of about ±0.045e.

Vibrational modes are more reliable for detecting charge order than for precise charge quantification.

Abstract

BEDT-TTF-based organic conductors host a number of ground states, tuned by electron repulsion from Mott and charge ordered insulators to superconductors. Knowing charge distribution on the molecular sites in the insulating state of these materials is a key to understanding the origin of these ground states. We survey and discuss the C=C stretching modes in BEDT-TTF based molecular conductors. These molecular vibrations are extremely crucial in characterization of charge-ordered insulators, and are recently linked to superconductivity in some compounds. Focusing on the known examples of BEDT-TTF$^{+0.5}$ salts, we analyse the reliability of the C=C stretching modes for the determination of charge ordering and absolute site charge. Considering the charge-ordered states, a prominent shift in frequency of 141 cm$^{-1}$ per elementary charge $e$ for $\nu_{27}(b_{1u})$ and 98 cm$^{-1}$$e$ for $\nu_2$($a_g$) can be clearly realised, however, the distribution resulting from different compounds span over 20 cm$^{-1}$. For nominal BEDT-TTF$^{+0.5}$ compounds, the distribution of the resonance also extends around 20 cm$^{-1}$, yielding an unexpected large uncertainty of $\Delta\rho~\approx~(~\pm~0.045)e$, which is presumably due to the influence of small differences in the structure. This highlights the limitations of charge-frequency relations to detect small deviations in absolute charge values on molecular lattice sites, and emphasises on the use of the relations to estimate charge-ordering, rather than absolute site charge.