Magnetic susceptibility of alkali-TCNQ salts and extended Hubbard models with bond order and charge density wave phases

TL;DR

This study models the magnetic susceptibility of alkali-TCNQ salts using extended Hubbard models, revealing their phases and electronic interactions, and comparing model parameters with optical data.

Contribution

It provides a quantitative analysis of magnetic susceptibility using Hubbard models, identifying phases and refining electronic interaction parameters for TCNQ salts.

Findings

Na and K salts are in the charge density wave phase.

Rb(II) salt is in the bond order wave phase.

Model parameters are smaller than those from optical data.

Abstract

The molar spin susceptibilities $\chi(T)$ of Na-TCNQ, K-TCNQ and Rb-TCNQ(II) are fit quantitatively to 450 K in terms of half-filled bands of three one-dimensional Hubbard models with extended interactions using exact results for finite systems. All three models have bond order wave (BOW) and charge density wave (CDW) phases with boundary $V = V_c(U)$ for nearest-neighbor interaction $V$ and on-site repulsion $U$. At high $T$, all three salts have regular stacks of $\rm TCNQ^-$ anion radicals. The $\chi(T)$ fits place Na and K in the CDW phase and Rb(II) in the BOW phase with $V \approx V_c$. The Na and K salts have dimerized stacks at $T < T_d$ while Rb(II) has regular stacks at 100K. The $\chi(T)$ analysis extends to dimerized stacks and to dimerization fluctuations in Rb(II). The three models yield consistent values of $U$, $V$ and transfer integrals $t$ for closely related $\rm TCNQ^-$ stacks. Model parameters based on $\chi(T)$ are smaller than those from optical data that in turn are considerably reduced by electronic polarization from quantum chemical calculation of $U$, $V$ and $t$ on adjacent $\rm TCNQ^-$ ions. The $\chi(T)$ analysis shows that fully relaxed states have reduced model parameters compared to optical or vibration spectra of dimerized or regular $\rm TCNQ^-$ stacks.