Ultrafast control of electronic states by a terahertz electric field pulse in the quasi-one-dimensional organic ferroelectric (TMTTF)2PF6

Abstract

A strong terahertz pulse is effective for controlling the macroscopic polarization in ferroelectrics. In the present study, we investigated the response of an organic molecular compound, namely ${(\mathrm{TMTTF})}_{2}\mathrm{P}{\mathrm{F}}_{6}$ (TMTTF: tetramethyltetrathiafulvalene), to a strong electric field using terahertz pulse-pump optical-reflectivity probe spectroscopy. This compound undergoes a transition from Mott insulator to charge-order insulator with lowering temperature, and exhibits electronic ferroelectricity in the charge-order phase. When the terahertz pulse is applied in the Mott-insulator phase, an ultrafast reflectivity change proportional to the square of the electric field waveform of the terahertz pulse emerges, which is attributed to the generation of charge disproportionation in each dimer and the resultant creation of macroscopic polarization. When the terahertz pulse is applied in the charge-order phase, an ultrafast reflectivity change proportional to the electric field waveform of the terahertz pulse is observed, which originates from the modulation of the original charge disproportionation and polarization. These ultrafast reflectivity changes can be ascribed to purely electronic responses. In the midinfrared region, where totally symmetric $({a}_{\mathrm{g}})$ modes of intramolecular vibrations coupled with intermolecular charge transfers exist, a large reflectivity change is commonly observed in the Mott-insulator and charge-order phases. To interpret this feature, we constructed a model that incorporates a charge-transfer transition and ${a}_{g}$-mode intramolecular vibrations. The analyses of the results with this model revealed that the change in the reflectivity spectrum by the terahertz electric field can be explained by the energy shift of the charge-transfer transition caused by the electric field-induced change of charge disproportionation in each dimer, and the transfer of the spectral weight from the intradimer charge-transfer (CT) transition to the interdimer CT transition resulting from the weakening of the dimerization. Our model can be used to analyze the optical responses to electric fields in various organic molecular compounds with electron-intramolecular vibration couplings.