A combined experimental and computational study of the pressure dependence of the vibrational spectrum of solid picene C_22H_14

We present high-quality optical data and density functional perturbation theory calculations for the vibrational spectrum of solid picene (C$_{22}$H$_{14}$) under pressure up to 8 GPa. First-principles calculations reproduce with a remarkable accuracy the pressure effects on both frequency and intensities of the phonon peaks experimentally observed . Through a detailed analysis of the phonon eigenvectors, We use the projection on molecular eigenmodes to unambiguously fit the experimental spectra, resolving complicated spectral structures, in a system with hundreds of phonon modes. With these projections, we can also quantify the loss of molecular character under pressure. Our results indicate that picene, despite a sim 20 % compression of the unit cell, remains substantially a molecular solid up to 8 GPa, with phonon modes displaying a smooth and uniform hardening with pressure. The Grueneisen parameter of the 1380 cm^{-1} a_1 Raman peak ($gamma_p=0.1$) is much lower than the effective value ($gamma_d=0.8$) due to K doping. This is an indication that the phonon softening in K doped samples is mainly due to charge transfer and electron-phonon coupling.

Accounting for spin fluctuations beyond LSDA in the density functional theory

We present a method to correct the magnetic properties of itinerant systems in local spin density approximation (LSDA) and we apply it to the ferromagnetic-paramagnetic transition under pressure in a typical itinerant system, Ni$_{3}$Al. We obtain a scaling of the critical fluctuations as a function of pressure equivalent to the one obtained within Moryias theory. Moreover we show that in this material the role of the bandstructure is crucial in driving the transition. Finally we calculate the magnetic moment as a function of pressure, and find that it gives a scaling of the Curie temperature that is in good agreement with the experiment. The method can be easily extended to the antiferromagnetic case and applied, for instance, to the Fe-pnictides in order to correct the LSDA magnetic moment.

Effects of magnetism and doping on the electron-phonon coupling in BaFe$_{2}$As$_{2}$

We calculate the effect of local magnetic moments on the electron-phonon coupling in BaFe$_{2}$As$_{2}+delta$ using the density functional perturbation theory. We show that the magnetism enhances the total electron-phonon coupling by $sim 50%$, up to $lambda lesssim 0.35$, still not enough to explain the high critical temperature, but strong enough to have a non-negligible effect on superconductivity, for instance, by frustrating the coupling with spin fluctuations and inducing order parameter nodes. The enhancement comes mostly from a renormalization of the electron-phonon matrix elements. We also investigate, in the rigid band approximation, the effect of doping, and find that $lambda$ versus doping does not mirror the behavior of the density of states; while the latter decreases upon electron doping, the former does not, and even increases slightly.

Electron-Phonon Properties of Pnictide Superconductors

In this paper we discuss the normal and superconducting state properties of two pnictide superconductors, LaOFeAs and LaONiAs, using Migdal-Eliashberg theory and density functional perturbation theory. For pure LaOFeAs, the calculated electron-phonon coupling constant $lambda=0.21$ and logarithmic-averaged frequency $omega_{ln}=206 K$, give a maximum $T_c$ of 0.8 K, using the standard Migdal-Eliashberg theory. Inclusion of multiband effects increases the Tc only marginally. To reproduce the experimental $T_c$, a 5-6 times larger coupling constant would be needed. Our results indicate that standard electron-phonon coupling is not sufficient to explain superconductivity in the whole family of Fe-As based superconductors. At the same time, the electron-phonon coupling in Ni-As based compounds is much stronger and its normal and superconducting state properties can be well described by standard Migdal-Eliashberg theory.

Pressure effects on the superconducting transition in nH-CaAlSi

We present a combined experimental and theoretical study of the effects of pressure on T_c of the hexagonal layered superconductors nH-CaAlSi (n = 1, 5, 6), where nH labels the different stacking variants that were recently discovered. Experimentally, the pressure dependence of T_c has been investigated by measuring the magnetic susceptibility of single crystals up to 10 kbar. In contrast to previous results on polycrystalline samples, single crystals with different stacking sequences display different pressure dependences of T_c. 1H-CaAlSi shows a decrease of T_c with pressure, whereas 5H and 6H-CaAlSi exhibit an increase of T_c with pressure. Ab-initio calculations for 1H, 5H and 6H -CaAlSi reveal that an ultrasoft phonon branch associated to out-of-plane vibrations of the Al-Si layers softens with pressure, leading to a structural instability at high pressures. For 1H-CaAlSi the softening is not sufficient to cause an increase of T_c, which is consistent with the present experiments, but adverse to previous reports. For 5H and 6H the softening provides the mechanism to understand the observed increase of T_c with pressure. Calculations for hypothetical 2H and 3H stacking variants reveal qualitative and quantitative differences.