The quest for electronic ferroelectricity in organic charge-transfer crystals

Organic ferroelectric materials are in demand in the growing field of environmentally friendly, lightweight electronics. Donor-Acceptor charge transfer crystals have been recently proposed as a new class of organic ferroelectrics, which may possess a new kind of ferroelectricity, the so-called electronic ferroelectricity, larger and with faster polarity switching in comparison with conventional, inorganic or organic, ferroelectrics. The current research aimed at achieving ambient conditions electronic ferroelectricity in organic charge transfer crystals is shortly reviewed, in such a way to evidence the emerging criteria that have to be fulfilled to reach this challenging goal.Comment: 6 pages, 7 figures. Proceedings of "2018 SUSTAINABLE INDUSTRIAL PROCESSING SUMMIT AND EXHIBITION

A new type of neutral-ionic interface in mixed-stack organic charge-tranfer crystals: Temperature induced ionicity change in ClMePD-DMeDCNQI

Raman and polarized infrared spectra of the mixed stack charge transfer crystal 2-chloro-5methyl-p-phenylendiamine- -2,5-dimethyl-dicyanoquinonediimine (ClMePD-DMeDCNQI) are reported as a function of temperature. A detailed spectral interpretation allows us to gain new insight into the temperature induced neutral-ionic transition in this compound. In particular, the crossing of the neutral-ionic borderline appears to be quite different from that of the few known temperature induced neutral-ionic phase transitions. First of all, the ionicity change is continuous. Furthermore, the onset of stack dimerization precedes, rather than accompanies, the neutral-ionic crossing. The (second order) phase transition is then driven by the dimerization, but the extent of dimerization is in turn affected by the ionicity change.Comment: LaTex (revTeX), 6 figures. Yields 10 pages postscript (including figures

A new type of neutral-ionic interface in mixed-stack organic charge-tranfer crystals: Temperature induced ionicity change in ClMePD-DMeDCNQI

Raman and polarized infrared spectra of the mixed stack charge transfer crystal 2-chloro-5methyl-p-phenylendiamine- -2,5-dimethyl-dicyanoquinonediimine (ClMePD-DMeDCNQI) are reported as a function of temperature. A detailed spectral interpretation allows us to gain new insight into the temperature induced neutral-ionic transition in this compound. In particular, the crossing of the neutral-ionic borderline appears to be quite different from that of the few known temperature induced neutral-ionic phase transitions. First of all, the ionicity change is continuous. Furthermore, the onset of stack dimerization precedes, rather than accompanies, the neutral-ionic crossing. The (second order) phase transition is then driven by the dimerization, but the extent of dimerization is in turn affected by the ionicity change.Comment: LaTex (revTeX), 6 figures. Yields 10 pages postscript (including figures

Pressure driven neutral-ionic transition in ClMePD-DMeDCNQI

Application of about 0.8 GPa pressure is sufficient to induce the neutral-ionic transition in the mixed stack charge-transfer crystal 2-chloro-5-methyl-$p$-phenylenediamine--2,5-dimethyl-dicyanoquinonediimine ({\CD}). The ionicity increases continuously from $\sim$ 0.35 at ambient conditions to $\sim$ 0.65 when the pressure is raised up to 2 GPa. Moreover, stack dimerization begins well before the crossing of the neutral-ionic interface. The evolution of the transition is similar to what observed in the temperature induced phase change in the same compound. (cond-mat/0101179) A distinguishing feature is represented by the simultaneous presence of domains of molecules with slightly different ionicities across the transition pressure. A comparison of the present example of pressure driven neutral-ionic transition with the well studied cases of tetrathiafulvalene--chloranil and of tetrathiafulvalene--2,5-dichloro-p-benzoquinone puts in evidence the remarkably different evolution of the three transitions.Comment: 6 pages in *.PS format, 5 figure

DMTTF-CA revisited: temperature-induced valence and structural instability

We report a detailed spectroscopic investigation of temperature-induced valence and structural instability of the mixed-stack organic charge-transfer (CT) crystal 4,4'-dimethyltetrathiafulvalene-chloranil (DMTTF-CA). DMTTF-CA is a derivative of tetrathiafulvalene-chloranil (TTF-CA), the first CT crystal exhibiting the neutral-ionic transition by lowering temperature. We confirm that DMTTF-CA undergoes a continuous variation of the ionicity on going from room temperature down to $\sim$ 20 K, but remains on the neutral side throughout. The stack dimerization and cell doubling, occurring at 65 K, appear to be the driving forces of the transition and of the valence instability. In a small temperature interval just below the phase transition we detect the coexistence of molecular species with slightly different ionicities. The Peierls mode(s) precursors of the stack dimerization are identified.Comment: 8 pages, 6 figures, Phys. Rev. B forma

Exact numerical diagonalization of one-dimensional interacting electrons nonadiabatically coupled to phonons

We study the role of non-adiabatic Holstein electron-phonon coupling on the neutral-ionic phase transition of charge transfer crystals which can be tuned from continuous to discontinuous, using exact numerical diagonalization. The variation of electronic properties through the transition is smoothed by nonadiabaticity. Lattice properties are strongly affected, and we observe both squeezing and antisqueezing, depending on details of the adiabatic potentials, and identify the quantum uncertainty of the phonons as the most sensitive measure of nonadiabaticity. The adiabatic limit is regular for a continuous transition but turns out completely inadequate near a discontinuous transition. The relevance of coherent state approaches is assessed critically.Comment: latex manuscript (7 pages), 3 eps figures; revised version, better discussion, one figure replaced; to be published in Europhys. Let

Cyclic Hypersequent System for Transitive Closure Logic

We propose a cut-free cyclic system for transitive closure logic (TCL) based on a form of hypersequents, suitable for automated reasoning via proof search. We show that previously proposed sequent systems are cut-free incomplete for basic validities from Kleene Algebra (KA) and propositional dynamic logic (PDL), over standard translations. On the other hand, our system faithfully simulates known cyclic systems for KA and PDL , thereby inheriting their completeness results. A peculiarity of our system is its richer correctness criterion, exhibiting ‘alternating traces’ and necessitating a more intricate soundness argument than for traditional cyclic proofs.</p

Uniform labelled calculi for preferential conditional logics based on neighbourhood semantics

International audienceThe preferential conditional logic PCL, introduced by Burgess, and its extensions are studied. First, a natural semantics based on neighbourhood models, which generalise Lewis' sphere models for counterfactual logics, is proposed. Soundness and completeness of PCL and its extensions with respect to this class of models are proved directly. Labelled sequent calculi for all logics of the family are then introduced. The cal-culi are modular and have standard proof-theoretical properties, the most important of which is admissibility of cut, that entails a syntactic proof of completeness of the calculi. By adopting a general strategy, root-first proof search terminates, thereby providing a decision procedure for PCL and its extensions. Finally, the semantic completeness of the calculi is established: from a finite branch in a failed proof attempt it is possible to extract a finite countermodel of the root sequent. The latter result gives a constructive proof of the finite model property of all the logics considered

Polymorphism, phonon dynamics and carrier-phonon coupling in pentacene

The crystal structure and phonon dynamics of pentacene is computed with the Quasi Harmonic Lattice Dynamics (QHLD) method, based on atom-atom potential. We show that two crystalline phases of pentacene exist, rather similar in thermodynamic stability and in molecular density. The two phases can be easily distinguished by Raman spectroscopy in the 10-100 cm-1 spectral region. We have not found any temperature induced phase transition, whereas a sluggish phase change to the denser phase is induced by pressure. The bandwidths of the two phases are slightly different. The charge carrier coupling to low-frequency phonons is calculated.Comment: 6 pages, 3 figures. Presented at ICFPAM-