Quasi-One-Dimensional Fermi Surface Nesting and Hidden Nesting Enable Multiple Kohn Anomalies in α-Uranium.

The topology of the Fermi surface controls the electronic response of a metal, including charge density wave (CDW) formation. A topology conducive for Fermi surface nesting (FSN) allows the electronic susceptibility χ_{0} to diverge and induce a CDW at wave vector q_{CDW}. Kohn extended the implications of FSN to show that the imaginary part of the lattice dynamical susceptibility χ_{L}^{''} also responds anomalously for all phonon branches at q_{CDW}-a phenomenon referred to as the Kohn anomaly. However, materials exhibiting multiple Kohn anomalies remain rare. Using first-principles simulations of χ_{0} and χ_{L}^{''}, and previous scattering measurements [Crummett et al., Phys. Rev. B 19, 6028 234 (1979)PRBMDO0163-1829], we show that α-uranium harbors multiple Kohn anomalies enabled by the combined effect of FSN and "hidden" nesting, i.e., nesting of electronic states above and below the Fermi surface. FSN and hidden nesting lead to a ridgelike feature in the real part of χ_{0}, allowing interatomic forces to modulate strongly and multiple Kohn anomalies to emerge. These results emphasize the importance of hidden nesting in controlling χ_{0} and χ_{L}^{''} to exploit electronic and lattice states and enable engineering of advanced materials, including topological Weyl semimetals and superconductors.

Orientational deformations leading to temperature-induced structural phase transition in Prehnite using Raman, Infrared, and Terahertz spectroscopy.

Understanding molecular and structural properties of naturally extracted minerals under varying thermodynamic parameters such as pressure (P) and temperature (T) helps us to explore vital information regarding various geological processes. Here, we present the comprehensive results of Raman, infrared (IR), and Terahertz (THz) spectroscopic investigations on Prehnite (Ca2Al(AlSi3O10)(OH)2) mineral from ambient (25 °C) to 1000 °C in the 6.6 - 4000 cm-1 wide spectral range. The results indicate a substantial distortion in orientation between AlO6 octahedron and SiO4 tetrahedron layer leads to the strengthening of hydrogen bonds (HBs) in the Prehnite structure around 800 °C. Consequently, the disappearance of Raman active modes and abrupt change in frequency (ω) of Far-IR modes (obtained using THz spectroscopy) around 800 °C are spectral signatures of symmetry change in the structure. Eventually, these orientational changes at the molecular level trigger structural phase transition around 800 °C, supported by X-ray diffraction (XRD) measurements. Thus, the present study depicts the pivotal role of inter- and intra-molecular interactions in Prehnite, which determines its bonding and structural characteristics and hence its physicochemical properties under diverse environments.

Magnetoelastic coupling and spin contributions to entropy and thermal transport in biferroic yttrium orthochromite.

Direct engineering of material properties through exploitation of spin, phonon, and charge-coupled degrees of freedom is an active area of development in materials science. However, the relative contribution of the competing orders to controlling the desired behavior is challenging to decipher. In particular, the independent role of phonons, magnons, and electrons, quasiparticle coupling, and relative contributions to the phase transition free energy largely remain unexplored, especially for magnetic phase transitions. Here, we study the lattice and magnetic dynamics of biferroic yttrium orthochromite using Raman, infrared, and inelastic neutron spectroscopy techniques, supporting our experimental results with first-principles lattice dynamics and spin-wave simulations across the antiferromagnetic transition atTN∼ 138 K. Spectroscopy data and simulations together with the heat capacity (Cp) measurements, allow us to quantify individual entropic contributions from phonons (0.01 ± 0.01kBatom-1), dilational (0.03 ± 0.01kBatom-1), and magnons (0.11 ± 0.01kBatom-1) acrossTN. High-resolution phonon measurements conducted in a magnetic field show that anomalousT-dependence of phonon energies acrossTNoriginates from magnetoelastic coupling. Phonon scattering is primarily governed by the phonon-phonon coupling, with little contribution from magnon-phonon coupling, short-range spin correlations, or magnetostriction effects; a conclusion further supported by our thermal conductivity measurements conducted up to 14 T, and phenomenological modeling.

Spectroscopic studies of temperature induced phase transitions in metal-organic complex trans-PtCl2(PEt3)2.

Tuning of molecular and electronic properties of Pt(II)-organic complexes have a profound effect on their applications in the fields of technology, pharmaceuticals and crystal engineering. Here, we present combined infrared and Raman spectroscopic investigations on trans-PtCl2(PEt3)2 systematically carried out at various temperatures from 300 to 4.2 K in a wide spectral range. The studies suggest drastic orientational changes of different moieties around 180 K and 130 K in the ligand groups attached to the central Pt atom. This is accompanied by a systematic strengthening of C-H⋯Cl hydrogen bonds in the 180-130 K temperature range. A discontinuous change in intensity, peak variations of modes and emergence of new modes across 180 K and 130 K in the lattice region are suggestive of a possible structural phase transition. It is interesting to note that the spectral signatures of the low temperature phase are different from those reported recently for the high pressure phase in this compound. These studies will be useful in better understanding the physico-chemical properties of metal-organic complexes in order to exploit their applications in various bio-chemical and technological fields.

Orientational Adaptations Leading to Plausible Phase Transitions in l-Leucine at Low Temperatures: Revealed by Infrared Spectroscopy.

Hydrogen bonding is essential for the stability of amino acids. A change in the geometry and conformation of hydrogen bonds in such molecular systems, for example, under varying thermodynamic conditions of temperature/pressure, may lead to subtle or drastic phase transitions. We demonstrate here the mechanism of temperature-induced phase transitions in the polycrystalline solid sample of l-leucine [(CH3)2-C(4)H-C(3)H2-C(2)H(C(1)OO-)(NH3+)], an "essential" amino acid, using in situ Fourier transform infrared spectroscopy in the temperature range 300-4.3 K. Unambiguous spectral signatures of preferred microstructural changes have been reported, which are linked to phase transitions at ∼150 and ∼240 K. The transition at 150 K is found to be associated with a sudden change in reorientation dynamics of the torsional vibrations of the (C3C4) group. In contrast, the transition at 240 K is associated with the conformational distortions in the NH3 group, which causes strengthening of the hydrogen bonds in the ac-plane forming two-dimensional sheets, well separated from each other in the b-direction. These findings pave the way toward settling the long-standing debate on the temperature-induced behavior of l-leucine as well as harnessing its physicochemical properties.

Perceptible isotopic effect in 3D-framework of α-glycine at low temperatures.

Glycine, the most fundamental amino acid, albeit studied for many decades, has kept researchers captivated with interesting structural variations relevant to important biological, astrophysical and technological applications. We report here a noticeable effect of deuteration on the three dimensional hydrogen bonding network of α-glycine using low temperature infrared absorption studies in a wide spectral range, corroborated with Raman scattering studies. These systematic studies in the range 300-4.2 K have demonstrated a relatively compact assembly of glycine molecules in the three dimensional bilayered structure of hydrogenated glycine (gly-h) at low temperatures. This is inferred from a remarkable temperature effect in the weak intra-bilayer hydrogen bond ~ along the b-axis, which strengthens upon cooling. A pronounced increase in the intensity of NH3 torsional and NH stretching modes has been observed. This is accompanied with a large rate of stiffening and softening respectively of these modes upon cooling and a change in slope across 210 K and 80 K. In contrast, the D---O hydrogen bond lengths in fully deuterated isotope (gly-d), as estimated using empirical correlation, show that the weak intra-bilayer hydrogen bond is not strengthened upon cooling down to 180 K, whereas the stronger intra-layer hydrogen bonds in the ac-plane become further strong. The ND3 torsional vibrations show no temperature effect. This implies a relatively stable two dimensional layered structure formed by strongly hydrogen bonded glycine sheets in the ac-plane. Below 180 K, similar qualitative trends have been obtained for the hydrogen bond lengths in the two isotopes. In addition, temperature induced variation of the characteristic "indicator" band of zwitterionic gly-h and gly-d has also been reported.