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Register a new userStrong terahertz radiation via rapid polarization reduction in photoinduced ionic-to-neutral transition of tetrathiafulvalene-p-chloranil
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Terahertz lights are usually generated through the optical rectification process within a femtosecond laser pulse in non-centrosymmetric materials. Here, we report a new generation mechanism of terahertz lights based upon a photoinduced phase transition (PIPT), in which an electronic structure is rapidly changed by a photoirradiation. When a ferroelectric organic molecular compound, tetrathiafulvalene-p-chloranil, is excited by a femtosecond laser pulse, the ionic-to-neutral transition is driven and simultaneously a strong terahertz radiation is produced. By analyzing the terahertz electric-field waveforms and their dependence on the polarization direction of the incident laser pulse, we demonstrate that the terahertz radiation originates from the ultrafast decrease of the spontaneous polarization in the photoinduced ionic-to-neutral transition. The efficiency of the observed terahertz radiation via the PIPT mechanism is found to be much higher than that via the optical rectification in the same material and in a typical terahertz emitter, ZnTe.
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We report a detailed spectroscopic study of the pressure induced neutral-ionic phase transition (NIT) of the mixed-stack charge-transfer (CT) crystal tetrathiafulvalene-chloranil (TTF-CA). We show that the pressure induced phase transition is still first-order and involves the presence of an intermediate disordered phase, defined by the coexistence of two species of different ionicity. Further application of pressure gradually converts this phase into an homogeneous ferroelectric phase with a single ionicity. In addition, we detect strong pretransitional phenomena which anticipate the intermediate phase and are indicative of a precursor dynamic regime dominated by fluctuations.
The neutral-to-ionic phase transition in the mixed-stack charge-transfer complex tetrathiafulvalene-p-chloranil (TTF-CA) has been studied by pressure-dependent infrared spectroscopy up to p=11 kbar and down to low temperatures, T = 10 K. By tracking the C=O antisymmetric stretching mode of CA molecules, we accurately determine the ionicity of TTF-CA in the pressure-temperature phase diagram. At any point the TTF-CA crystal bears only a single ionicity; there is no coexistence region or an exotic high-pressure phase. Our findings shed new light on the role of electron-phonon interaction in the neutral-ionic transition.
Transition metal doping is known to increase the photosensitivity to visible light for photocatalytically active ZnO. We report on the electronic structure of nano-crystalline Fe:ZnO, which has recently been shown to be an efficient photocatalyst. The photo-activity of ZnO reduces Fe from 3+ to 2+ in the surface region of the nano-crystalline material. Electronic states corresponding to low-spin Fe 2+ are observed and attributed to crystal field modification at the surface. These states can be important for the photocatalytic sensitivity to visible light due to their deep location in the ZnO bandgap. X-ray absorption and x-ray photoemission spectroscopy suggest that Fe is only homogeneously distributed for concentrations up to 3%. Increased concentrations does not result in a higher concentration of Fe ions in the surface region. This is a crucial factor limiting the photocatalytic functionality of ZnO, where the most efficient doping concentration have been shown to be 2-4% for Fe doping. Using resonant photoemission spectroscopy we determine the location of Fe 3d states with sensitivity to the charge states of the Fe ion even for multi-valent and multi-coordinated Fe.
Ferroelectrics that are also ionic conductors offer possibilities for novel applications with high tunability, especially if the same atomic species causes both phenomena. In particular, at temperatures just below the Curie temperature, polarized states may be sustainable as the mobile species is driven in a controlled way over the energy barrier that governs ionic conduction, resulting in unique control of the polarization. This possibility was recently demonstrated in CuInP2S6, a layered ferroelectric ionic conductor in which Cu ions cause both ferroelectricity and ionic conduction. Here, we show that the commonly used approach to calculate the polarization of evolving atomic configurations in ferroelectrics using the modern theory of polarization, namely concerted (synchronous) migration of the displacing ions, is not well suited to describe the polarization evolution as the Cu ions cross the van der Waals gaps. We introduce an asynchronous Cu-migration scheme, which reflects the physical process by which Cu ions migrate, resolves the difficulties, and describes the polarization evolution both for normal ferroelectric switching and for transitions across the van der Waals gaps, providing a single framework to discuss ferroelectric ionic conductors.
Electronic polarization and charge transfer effects play a crucial role in thermodynamic, structural and transport properties of room-temperature ionic liquids (RTILs). These non-additive interactions constitute a useful tool for tuning physical chemical behavior of RTILs. Polarization and charge transfer generally decay as temperature increases, although their presence should be expected over an entire condensed state temperature range. For the first time, we use three popular pyridinium-based RTILs to investigate temperature dependence of electronic polarization in RTILs. Atom-centered density matrix propagation molecular dynamics, supplemented by a weak coupling to an external bath, is used to simulate the temperature impact on system properties. We show that, quite surprisingly, non-additivity in the cation-anion interactions changes negligibly between 300 and 900 K, while the average dipole moment increases due to thermal fluctuations of geometries. Our results contribute to the fundamental understanding of electronic effects in the condensed phase of ionic systems and foster progress in physical chemistry and engineering.
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