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Title: Optical Study of Electronic Structure and Photoinduced Dynamics in the Organic Alloy System [(EDO-TTF)₀.₈₉(MeEDO-TTF)₀.₁₁]₂PF₆
Authors: Ishikawa, Tadahiko
Urasawa, Yohei
Shindo, Taiki
Okimoto, Yoichi
Koshihara, Shin-ya
Tanaka, Seiichi
Onda, Ken
Hiramatsu, Takaaki
Nakano, Yoshiaki  kyouindb  KAKEN_id  orcid https://orcid.org/0000-0003-3616-7286 (unconfirmed)
Tanaka, Koichiro
Yamochi, Hideki
Author's alias: 平松, 孝章
中野, 義明
田中, 耕一郎
矢持, 秀起
Keywords: photoinduced dynamics
metal–insulator transition
charge ordering
1/4-filled band system
2kF modulation
electron correlation
electron–lattice interaction
electron molecular interaction
donor–anion interaction
organic alloy
Issue Date: 20-Mar-2019
Publisher: MDPI AG
Journal title: Applied Sciences
Volume: 9
Issue: 6
Thesis number: 1174
Abstract: Over the past two decades (EDO-TTF)₂PF₆(EDO-TTF = 4, 5-ethylenedioxytetrathiafulvalene), which exhibits a metal–insulator (M–I) phase transition with charge–ordering (CO), has been investigated energetically because of attractive characteristics that include ultrafast and massive photoinduced spectral and structural changes. In contrast, while its crystal structure has much in common with the (EDO-TTF)₂PF₆ crystal, the organic alloy system of [(EDO-TTF)₀.₈₉(MeEDO-TTF)₀.₁₁]₂PF₆ (MeEDO-TTF = 4, 5-ethylenedioxy-4′-methyltetrathiafulvalene) exhibits a quite different type of M–I phase transition that is attributed to Peierls instability. Here, an optical study of the static absorption spectra and the time-resolved changes in the absorption spectra of [(EDO-TTF)₀.₈₉(MeEDO-TTF)₀.₁₁]₂PF₆ are reported. The observed absorption spectra related to the electronic structure are highly anisotropic. With a reduction in temperature (T), the opening of a small optical gap and a small shift in the center frequency of the C=C stretching mode are observed along with the M–I phase transition. Additionally, photoinduced transient states have been assigned based on their relaxation processes and transient intramolecular vibrational spectra. Reflecting small valence and structural changes and weak donor–anion interactions, a photoinduced transient state that is similar to the thermal-equilibrium high-T metallic phase appears more rapidly in the alloy system than that in (EDO-TTF)₂PF₆.
Rights: © 2019 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
URI: http://hdl.handle.net/2433/240614
DOI(Published Version): 10.3390/app9061174
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