Abstract
This paper reviews charge ordering in the organic conductors, β″-(BEDT-TTF) (TCNQ), θ-(BEDT-TTF)2X, and α-(BEDT-TTF)2X. Here, BEDT-TTF and TCNQ represent bis(ethylenedithio)tetrathiafulvalene and 7,7,8,8-tetracyanoquinodimethane, respectively. These compounds, all of which have a quarter-filled band, were evaluated using infrared and Raman spectroscopy in addition to optical conductivity measurements. It was found that β″-(BEDT-TTF)(TCNQ) changes continuously from a uniform metal to a charge-ordered metal with increasing temperature. Although charge disproportionation was clearly observed, long-range charge order is not realized. Among six θ-type salts, four compounds with a narrow band show the metal-insulator transition. However, they maintain a large amplitude of charge order (Δρ~0.6) in both metallic and insulating phases. In the X = CsZn(SCN)4 salt with intermediate bandwidth, the amplitude of charge order is very small (Δρ < 0.07) over the whole temperature range. However, fluctuation of charge order is indicated in the Raman spectrum and optical conductivity. No indication of the fluctuation of charge order is found in the wide band X = I3 salt. In α-(BEDT-TTF)2I3 the amplitude of charge order changes discontinuously from small amplitude at high temperature to large amplitude (Δρmax~0.6) at low temperature. The long-range charge-ordered state shows ferroelectric polarization with fast optical response. The fluctuation of multiple stripes occurs in the high-temperature metallic phase. Among α-(BEDT-TTF)2MHg(SCN)4 (X = NH4, K, Rb, Tl), the fluctuation of charge order is indicated only in the X = NH4 salt. α′-(BEDT-TTF)2IBr2 shows successive phase transitions to the ferroelectric state keeping a large amplitude of charge order (Δρmax~0.8) over the whole temperature range. It was found that the amplitude and fluctuation of charge order in these compounds is enhanced as the kinetic energy (bandwidth) decreases.
Highlights
Vibrational spectroscopy is a powerful tool to detect the valence of molecules in organic charge-transfer salts
As the chemical bond is usually much stronger than intermolecular interactions, the vibrational frequency and symmetry of a free molecule is approximately preserved in the solid state except in the case where a strong vibronic interaction occurs between a vibrational mode and a low-energy electronic state
Vibrational spectroscopy was applied to mixed-valence compounds of TCNQ [4], where one of the CN stretching modes of TCNQ was utilized as the probe
Summary
Vibrational spectroscopy is a powerful tool to detect the valence of molecules in organic charge-transfer salts. The author reviews infrared, Raman, and optical conductivity measurements of BEDT-TTF salts, which, apart from β′′-(BEDT-TTF)(TCNQ), have a herringbone arrangement This latter compound is included in this paper, because its unique behavior is necessary for understanding the metallic phase of θ- and α-type BEDT-TTF salts.
Sign-in/Register to view highlights & summary Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
