BEDT-TTF organic superconductors: the entangled role of phonons

We calculate the lattice phonons and the electron-phonon coupling of the organic superconductor \kappa-(BEDT-TTF)_2 I_3, reproducing all available experimental data connected to phonon dynamics. Low-frequency intra-molecular vibrations are strongly mixed to lattice phonons. Both acoustic and optical phonons are appreciably coupled to electrons through the modulation of the hopping integrals (e-LP coupling). By comparing the results relevant to superconducting \kappa- and \beta-(BEDT-TTF)_2 I_3, we show that electron-phonon coupling is fundamental to the pairing mechanism. Both e-LP and electron-molecular vibration (e-MV) coupling are essential to reproduce the critical temperatures. The e-LP coupling is stronger, but e-MV is instrumental to increase the average phonon frequency.Comment: 4 pages, including 4 figures. Published version, with Ref. 17 corrected after publicatio

Quasi-degenerate self-trapping in one-dimensional charge transfer exciton

The self-trapping by the nondiagonal particle-phonon interaction between two quasi-degenerate energy levels of excitonic system, is studied. We propose this is realized in charge transfer exciton, where the directions of the polarization give the quasi-degeneracy. It is shown that this mechanism, unlike the conventional diagonal one, allows a coexistence and resonance of the free and self-trapped states even in one-dimensional systems and a quantitative theory for the optical properties (light absorption and time-resolved luminescence) of the resonating states is presented. This theory gives a consistent resolution for the long-standing puzzles in quasi-one-dimensional compound A-PMDA.Comment: accepted to Phys. Rev. Letter

Effect of Benzoic Acids on Barite and Calcite Precipitation

The effect of various benzoic acids on the precipitation of barite (BaSO4) and calcite (CaCO3) was investigated. The acids varied in the number of carboxylate groups, from dibenzoic acids (phthalic, isophthalic, and terephthalic) through to the hexabenzoic acid (mellitic acid). It was found that the stereochemistry of the dibenzoic acids was important, as was the pH of the solution (trimesic acid was used as a test case and showed that greatest inhibition was achieved with all carboxylate groups deprotonated). Interestingly, for both the calcite and barite systems, mellitic acid was found to be both a potent inhibitor and a significant crystal growth modifier. In the case of barite, the presence of mellitic acid produced nanoparticles that agglomerated. The nanoparticles were found to be 20 nm in size from X-ray diffraction (XRD) line width analysis and 20-50 nm from transmission electron microscopy (TEM). Humic acid was also tested and found to form bundled fibers of barium sulfate

Thermal Behavior of Benzoic Acid/Isonicotinamide Binary Cocrystals

YesA comprehensive study of the thermal behavior of the 1:1 and 2:1 benzoic acid/isonicotinamide cocrystals is reported. The 1:1 material shows a simple unit cell expansion followed by melting upon heating. The 2:1 crystal exhibits more complex behavior. Its unit cell first expands upon heating, as a result of C–H···π interactions being lengthened. It then is converted into the 1:1 crystal, as demonstrated by significant changes in its X-ray diffraction pattern. The loss of 1 equiv of benzoic acid is confirmed by thermogravimetric analysis–mass spectrometry. Hot stage microscopy confirms that, as intuitively expected, the transformation begins at the crystal surface. The temperature at which conversion occurs is highly dependent on the sample mass and geometry, being reduced when the sample is under a gas flow or has a greater exposed surface area but increased when the heating rate is elevated

Diffusion Monte Carlo Study of Para -Diiodobenzene Polymorphism Revisited

We revisit our investigation of the diffusion Monte Carlo (DMC) simulation of p-DIB molecular crystal polymorphism. [J. Phys. Chem. Lett. 2010, 1, 1789-1794] We perform, for the first time, a rigorous study of finite-size effects and choice of nodal surface on the prediction of polymorph stability in molecular crystals using fixed-node DMC. Our calculations are the largest which are currently feasible using the resources of the K computer and provide insights into the formidable challenge of predicting such properties from first principles. In particular, we show that finite-size effects can influence the trial nodal surface of a small (1×1×1) simulation cell considerably. We therefore repeated our DMC simulations with a 1×3×3 simulation cell, which is the largest such calculation to date. We used a DFT nodal surface generated with the PBE functional and we accumulated statistical samples with ∼6.4×105 core-hours for each polymorph. Our final results predict a polymorph stability consistent with experiment, but indicate that results in our previous paper were somewhat fortuitous. We analyze the finite-size errors using model periodic Coulomb (MPC) interactions and kinetic energy corrections, according to the CCMH scheme of Chiesa, Ceperley, Martin, and Holzmann. We investigate the dependence of the finite-size errors on different aspect ratios of the simulation cell (k-mesh convergence) in order to understand how to choose an appropriate ratio for the DMC calculations. Even in the most expensive simulations currently possible, we show that the finite size errors in the DMC total energies are far larger than the energy difference between the two polymorphs, although error cancellation means that the polymorph prediction is accurate. Finally, we found that the T-move scheme is essential for these massive DMC simulations in order to circumvent population explosions and large time-step biases.Chemistry and Chemical Biolog