Low temperature structural effects in the (TMTSF)$_2$PF$_6$ and AsF$_6$ Bechgaard salts

TL;DR

This study investigates low-temperature structural effects in (TMTSF)$_2$PF$_6$ and AsF$_6$ salts, revealing how deuteration influences lattice dynamics, low-frequency modes, and structural changes around 55 K, with implications for understanding their physical properties.

Contribution

The paper provides the first detailed low-temperature structural analysis of deuterated and hydrogenated (TMTSF) salts, highlighting the impact of deuteration as negative pressure and identifying characteristic librational frequencies.

Findings

Deuteration acts as negative pressure of 500 MPa.

Identified low-frequency methyl group modes at 8.3 K and 6.7 K.

Observed structural change around 55 K linked to F...D bonds.

Abstract

We present a detailed low-temperature investigation of the statics and dynamics of the anions and methyl groups in the organic conductors (TMTSF)$_2$PF$_6$ and (TMTSF)$_2$AsF$_6$ (TMTSF : tetramethyl-tetraselenafulvalene). The 4 K neutron scattering structure refinement of the fully deuterated (TMTSF)$_2$PF$_6$-D12 salt allows locating precisely the methyl groups at 4 K. This structure is compared to the one of the fully hydrogenated (TMTSF)$_2$PF$_6$-H12 salt previously determined at the same temperature. Surprisingly it is found that deuteration corresponds to the application of a negative pressure of 5 x 10$^2$ MPa to the H12 salt. Accurate measurements of the Bragg intensity show anomalous thermal variations at low temperature both in the deuterated PF$_6$ and AsF$_6$ salts. Two different thermal behaviors have been distinguished. Low-Bragg-angle measurements reflect the presence of low-frequency modes at characteristic energies {\theta}$_E$ = 8.3 K and {\theta}$_E$ = 6.7 K for the PF$_6$-D12 and AsF$_6$-D12 salts, respectively. These modes correspond to the low-temperature methyl group motion. Large-Bragg-angle measurements evidence an unexpected structural change around 55 K which probably corresponds to the linkage of the anions to the methyl groups via the formation of F...D-CD2 bonds observed in the 4 K structural refinement. Finally we show that the thermal expansion coefficient of (TMTSF)$_2$PF$_6$ is dominated by the librational motion of the PF$_6$ units. We quantitatively analyze the low-temperature variation of the lattice expansion via the contribution of Einstein oscillators, which allows us to determine for the first time the characteristic frequency of the PF6 librations: {\theta}$_E$ = 50 K and {\theta}$_E$ = 76 K for the PF$_6$-D12 and PF$_6$-H12 salts, respectively.