The reflectivity of large single crystals of protonated and deuterated (TMTSF)₂Re0₄ and (TMTSF)₂BF₄ has been measured from ≈ 30 cm-¹ to ≈ 8000 cm-¹ using a Bruker IFS 113V Fourier Transform Interferometer for E / a and E / b' above and below the metal--insulator transitions at 177 K and 39 K respectively. The infrared powder absorption spectra of protonated and deuterated (TMTSF)₂Re0₄ has been measured from 200 cm˗¹ to 2000 cm˗¹. The Kramers-Kronig optical conductivity has been calculated from the reflectivity using Drude extrapolations to high frequency. The results for the conductivity
for E / a show a one-dimensional density of states, characteristic of a one-dimensional semiconductor with strong electron-phonon coupling, with the vibrations appearing as resonances below the gap and as antiresonances above. The E / b' conductivity is smaller by almost two orders of magnitude than that for E / a, but displays the same semiconducting
behavior. The phonons active in the E / b' polarization appear only as resonances.
A normal coordinate analysis has been performed for protonated and deuterated TMTSF⁰ and TMTSF⁺. The results have been used to infer the frequencies of vibration and the deuterium shifts of TMTSF⁺⁰ׄ⁵. The molecular frequencies of vibration have been assigned on the basis of their observed frequencies and optical polarization, as well as their deuterium shifts. Some external phonons have also been assigned. The observation that many of the internal and external vibrations are split is due to the eightfold increase in the size of the unit cell (and subsequent reduction of the Brillouin zone) below the metal-insulator transition.
The optical properties of the semiconducting state have been modelled for a one--dimensional molecular conductor with a twofold-commensurate charge-density wave, which accurately reproduces the effects of the lattice dimerization and the potential due to the anion chains. The calculations yield the electron-molecular-vibrational coupling constants for the totally symmetric a[formula omitted] vibrations of the TMTSF molecule. The model also yields a transfer integral of 1400 cm-¹ for both materials and semiconducting energy gaps of 2Δ = 1700 cm˗¹ and 2Δ = 1120 cm˗¹ for (TMTSF)₂ReO₄ and (TMTSF)₂BF₄ respectively. The optical conductivity in the E / b' polarization has been discussed in -terms of a two-dimensional band structure with anisotropic transfer integrals. The band structure calculations show the same general features as the measured spectra. / Science, Faculty of / Physics and Astronomy, Department of / Graduate
| Identifer | oai:union.ndltd.org:UBC/oai:circle.library.ubc.ca:2429/30641 |
| Date | January 1990 |
| Creators | Homes, Christopher C. (Christopher Craver) |
| Publisher | University of British Columbia |
| Source Sets | University of British Columbia |
| Language | English |
| Detected Language | English |
| Type | Text, Thesis/Dissertation |
| Rights | For non-commercial purposes only, such as research, private study and education. Additional conditions apply, see Terms of Use https://open.library.ubc.ca/terms_of_use. |
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