Effect of pressure on the Raman modes of antimony

The effect of pressure on the zone-center optical phonon modes of antimony in the A7 structure has been investigated by Raman spectroscopy. The A_g and E_g frequencies exhibit a pronounced softening with increasing pressure, the effect being related to a gradual suppression of the Peierls-like distortion of the A7 phase relative to a cubic primitive lattice. Also, both Raman modes broaden significantly under pressure. Spectra taken at low temperature indicate that the broadening is at least partly caused by phonon-phonon interactions. We also report results of ab initio frozen-phonon calculations of the A_g and E_g mode frequencies. Presence of strong anharmonicity is clearly apparent in calculated total energy versus atom displacement relations. Pronounced nonlinearities in the force versus displacement relations are observed. Structural instabilities of the Sb-A7 phase are briefly addressed in the Appendix.Comment: 10 pages, 8 figure

How chemistry controls electron localization in 3d1 perovskites: A Wannier-function study

In the series of 3d1 t2g perovskites, SrVO3--CaVO3--LaTiO3--YTiO3 the transition-metal d electron becomes increasingly localized and undergoes a Mott transition between CaVO3 and LaTiO3. By defining a low-energy Hubbard Hamiltonian in the basis of Wannier functions for the t2g LDA band and solving it in the single-site DMFT approximation, it was recently shown[1] that simultaneously with the Mott transition there occurs a strong suppression of orbital fluctuations due to splitting of the t2g levels. The present paper reviews and expands this work, in particular in the direction of exposing the underlying chemical mechanisms by means of ab initio LDA Wannier functions generated with the NMTO method. The Wannier functions for the t2g band exhibit covalency between the transition-metal t2g, the large cation-d, and the oxygen-p states; this covalency, which increases along the series, turns out to be responsible not only for the splittings of the t2g levels, but also for non-cubic perturbations of the hopping integrals, both of which are decisive for the Mott transition. We find good agreement with the optical and photoemission spectra, with the crystal-field splittings and orbital polarizations recently measured for the titanates, and with the metallization volume for LaTiO3. The metallization volume for YTiO3 is predicted. Using super-exchange theory, we reproduce the observed magnetic orders in LaTiO3 and YTiO3, but the results are sensitive to detail, in particular for YTiO3 which, without the Jahn-Teller distortion, would be AFM C- or A-type, rather than FM. Finally, we show that it possible to unfold the orthorhombic t2g LDA bandstructure to a pseudocubic zone. In this zone, the lowest band is separated from the two others by a direct gap and has a width, W_I, which is significantly smaller than that, W, of the entire t2g band. The progressive GdFeO3-type distortion favours electron localization by decreasing W, by increasing the splitting of the t2g levels and by decreasing W_I. Our conclusions concerning the roles of GdFeO3-type and JT distortions agree with those of Mochizuki and Imada [2].Comment: Published version, final. For high resolution figures see http://www.fkf.mpg.de/andersen/docs/pub/abstract2004+/pavarini_02.pd

Raman spectra of MgB2 at high pressure and topological electronic transition

Raman spectra of the MgB2 ceramic samples were measured as a function of pressure up to 32 GPa at room temperature. The spectrum at normal conditions contains a very broad peak at ~590 cm-1 related to the E2g phonon mode. The frequency of this mode exhibits a strong linear dependence in the pressure region from 5 to 18 GPa, whereas beyond this region the slope of the pressure-induced frequency shift is reduced by about a factor of two. The pressure dependence of the phonon mode up to ~ 5GPa exhibits a change in the slope as well as a "hysteresis" effect in the frequency vs. pressure behavior. These singularities in the E2g mode behavior under pressure support the suggestion that MgB2 may undergo a pressure-induced topological electronic transition.Comment: 2 figure

Structural and superconducting properties of MgB2−x_{2-x}Bex_x

We prepared MgB$_{2-x}$Be$_{x}$ ($x=0$, 0.2, 0.3, 0.4, and 0.6) samples where B is substituted with Be. MgB$_{2}$ structure is maintained up to $x=0.6$. In-plane and inter-plane lattice constants were found to decrease and increase, respectively. Superconducting transition temperature $T_{c}$ decreases with $x$. We found that the $T_{c}$ decrease is correlated with in-plane contraction but is insensitive to carrier doping, which is consistent with other substitution studies such as Mg$_{1-x}$Al$_{x}$B$_{2}$ and MgB$_{2-x}$C$_{x}$. Implication of this work is discussed in terms of the 2D nature of $\sigma$-band.Comment: 3 pages,4 figures, to be published in Phys. Rev.

Mixing of magnetic and phononic excitations in incommensurate Spin-Peierls systems

We analyze the excitation spectra of a spin-phonon coupled chain in the presence of a soliton. This is taken as a microscopic model of a Spin-Peierls material placed in a high magnetic field. We show, by using a semiclassical approximation in the bosonized representation of the spins that a trapped magnetic state obtained in the adiabatic approximation is destroyed by dynamical phonons. Low energy states are phonons trapped by the soliton. When the magnetic gap is smaller than the phonon frequencies the only low energy state is a mixed magneto-phonon state with the energy of the gap. We emphasize that our results are relevant for the Raman spectra of the inorganic Spin-Peierls material CuGeO$_3$.Comment: 5 pages, latex, 2 figures embedded in the tex

Far-Infrared Spectroscopy in Spin-Peierls Compound CuGeO_3 under High Magnetic Fields

Polarized far-infrared (FIR) spectroscopic measurements and FIR magneto-optical studies were performed on the inorganic spin-Peierls compound CuGeO_3. An absorption line, which was found at 98 cm$^{-1}$ in the dimerized phase (D phase), was assigned to a folded phonon mode of B$_{3u}$ symmetry. The splitting of the folded mode into two components in the incommensurate phase (IC phase) has been observed for the first time. A new broad absorption centered at 63 cm$^{-1}$ was observed only in the ${\bf E}\parallel b$ axis polarization, which was assigned to a magnetic excitation from singlet ground state to a continuum state.Comment: 9 pages multicolREVTeX, 10 figure

Spin-phonon coupled modes in the incommensurate phases of doped CuGeO3_{3}

The doping effect of the folded phonon mode at 98 cm$^{-1}$ was investigated on the Si-doped CuGeO$_3$ by magneto-optical measurements in far-infrared (FIR) region under high magnetic field. The folded phonon mode at 98 cm$^{-1}$ appears not only in the dimerized (D) phase but also in the dimerized-anitiferromagnetic (DAF) phase on the doped CuGeO$_3$. The splitting was observed in the incommensurate (IC) phase and the antiferromagnetically ordered incommensurate (IAF) phase above $H_C$. The split-off branches exhibit different field dependence from that of the pure CuGeO$_3$ in the vicinity of $H_C$, and the discrepancy in the IAF phase is larger than that in the IC phase. It is caused by the interaction between the solitons and the impurities.Comment: 7 pages, 4 figures, resubmitted to Phys. Rev.

Simple Metals at High Pressure

In this lecture we review high-pressure phase transition sequences exhibited by simple elements, looking at the examples of the main group I, II, IV, V, and VI elements. General trends are established by analyzing the changes in coordination number on compression. Experimentally found phase transitions and crystal structures are discussed with a brief description of the present theoretical picture.Comment: 22 pages, 4 figures, lecture notes for the lecture given at the Erice course on High-Pressure Crystallography in June 2009, Sicily, Ital

Raman spectrum and lattice parameters of MgB2 as a function of pressure

We report Raman spectra and synchrotron x-ray diffraction measurements of lattice parameters of polycrystalline MgB2 under hydrostatic pressure conditions up to 15 GPa. An anomalously broadened Raman band at 620 cm-1 is observed that exhibits a large linear pressure shift of its frequency. The large mode damping and Gruneisen parameter indicate a highly anharmonic nature of the mode, broadly consistent with theoretical predictions for the E2g in-plane boron stretching mode. The results obtained may provide additional constraints on the electron-phonon coupling in the system.Comment: 3 pages, 3 figure

Excitations of the field-induced soliton lattice in CuGeO3

Here we report the first inelastic neutron scattering study of the magnetic excitations in the incommensurate phase of a spin-Peierls material. The results on CuGeO3 provide direct evidence of a finite excitation gap, two sharp magnetic excitation branches and a very low-lying excitation which is identified as a phason mode, the Goldstone mode of the incommensurate soliton lattice.Comment: 5 pages, revtex, 4 figures (*.eps), win-zippe