Infrared spectroscopic studies on unoriented single-walled carbon nanotube films under hydrostatic pressure

The electronic properties of as-prepared and purified unoriented single-walled carbon nanotube films were studied by transmission measurements over a broad frequency range (far-infrared up to visible) as a function of temperature (15 K - 295 K) and external pressure (up to 8 GPa). Both the as-prepared and the purified SWCNT films exhibit nearly temperature-independent properties. With increasing pressure the low-energy absorbance decreases suggesting an increasing carrier localization due to pressure-induced deformations. The energy of the optical transitions in the SWCNTs decreases with increasing pressure, which can be attributed to pressure-induced hybridization and symmetry-breaking effects. We find an anomaly in the pressure-induced shift of the optical transitions at $\sim$2 GPa due to a structural phase transition.Comment: 13 pages, 15 figure

Group delay in THz spectroscopy with ultra-wideband log-spiral antennae

We report on the group delay observed in continuous-wave terahertz spectroscopy based on photomixing with phase-sensitive homodyne detection. We discuss the different contributions of the experimental setup to the phase difference \Delta\phi(\nu) between transmitter arm and receiver arm. A simple model based on three contributions yields a quantitative description of the overall behavior of \Delta\phi(\nu). Firstly, the optical path-length difference gives rise to a term linear in frequency. Secondly, the ultra-wideband log-spiral antennae effectively radiate and receive in a frequency-dependent active region, which in the most simple model is an annular area with a circumference equal to the wavelength. The corresponding term changes by roughly 6 pi between 100 GHz and 1 THz. The third contribution stems from the photomixer impedance. In contrast, the derivative (d\Delta\phi / d\nu) is dominated by the contribution of periodic modulations of \Delta\phi(\nu) caused by standing waves, e.g., in the photomixers' Si lenses. Furthermore, we discuss the Fourier-transformed spectra, which are equivalent to the waveform in a time-domain experiment. In the time domain, the group delay introduced by the log-spiral antennae gives rise to strongly chirped signals, in which low frequencies are delayed. Correcting for the contributions of antennae and photomixers yields sharp peaks or "pulses" and thus facilitates a time-domain-like analysis of our continuous-wave data.Comment: 7 pages, 7 figure

Self-normalizing phase measurement in multimode terahertz spectroscopy based on photomixing of three lasers

Photomixing of two near-infrared lasers is well established for continuous-wave terahertz spectroscopy. Photomixing of three lasers allows us to measure at three terahertz frequencies simultaneously. Similar to Fourier spectroscopy, the spectral information is contained in an nterferogram, which is equivalent to the waveform in time-domain spectroscopy. We use one fixed terahertz frequency \nu_ref to monitor temporal drifts of the setup, i.e., of the optical path-length difference. The other two frequencies are scanned for broadband high-resolution spectroscopy. The frequency dependence of the phase is obtained with high accuracy by normalizing it to the data obtained at \nu_ref, which eliminates drifts of the optical path-length difference. We achieve an accuracy of about 1-2 microns or 10^{-8} of the optical path length. This method is particularly suitable for applications in nonideal environmental conditions outside of an air-conditioned laboratory.Comment: 5 pages, 5 figure

Polaron physics and crossover transition in magnetite probed by pressure-dependent infrared spectroscopy

The optical properties of magnetite at room temperature were studied by infrared reflectivity measurements as a function of pressure up to 8 GPa. The optical conductivity spectrum consists of a Drude term, two sharp phonon modes, a far-infrared band at around 600 cm$^{-1}$, and a pronounced mid-infrared absorption band. With increasing pressure both absorption bands shift to lower frequencies and the phonon modes harden in a linear fashion. Based on the shape of the MIR band, the temperature dependence of the dc transport data, and the occurrence of the far-infrared band in the optical conductivity spectrum the polaronic coupling strength in magnetite at room temperature should be classified as intermediate. For the lower-energy phonon mode an abrupt increase of the linear pressure coefficient occurs at around 6 GPa, which could be attributed to minor alterations of the charge distribution among the different Fe sites.Comment: 7 pages, 7 figure

The Future of the Correlated Electron Problem

The understanding of material systems with strong electron-electron interactions is the central problem in modern condensed matter physics. Despite this, the essential physics of many of these materials is still not understood and we have no overall perspective on their properties. Moreover, we have very little ability to make predictions in this class of systems. In this manuscript we share our personal views of what the major open problems are in correlated electron systems and we discuss some possible routes to make progress in this rich and fascinating field. This manuscript is the result of the vigorous discussions and deliberations that took place at Johns Hopkins University during a three-day workshop January 27, 28, and 29, 2020 that brought together six senior scientists and 46 more junior scientists. Our hope, is that the topics we have presented will provide inspiration for others working in this field and motivation for the idea that significant progress can be made on very hard problems if we focus our collective energies.Comment: 55 pages, 19 figure

Pressure induced enhancement of the magnetic ordering temperature in rhenium(IV) monomers

Materials that demonstrate long-range magnetic order are synonymous with information storage and the electronics industry, with the phenomenon commonly associated with metals, metal alloys or metal oxides and sulfides. A lesser known family of magnetically ordered complexes are the monometallic compounds of highly anisotropic d-block transition metals; the ‘transformation’ from isolated zero-dimensional molecule to ordered, spin-canted, three-dimensional lattice being the result of through-space interactions arising from the combination of large magnetic anisotropy and spin-delocalization from metal to ligand which induces important intermolecular contacts. Here we report the effect of pressure on two such mononuclear rhenium(IV) compounds that exhibit long-range magnetic order under ambient conditions via a spin canting mechanism, with Tc controlled by the strength of the intermolecular interactions. As these are determined by intermolecular distance, ‘squeezing’ the molecules closer together generates remarkable enhancements in ordering temperatures, with a linear dependence of Tc with pressure

Synthesis and properties of the heterospin (S1 = S2 = 1/2) radical-ion salt bis(mesitylene)molybdenum(I) [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazolidyl

The authors are grateful to the Presidium of the Russian Academy of Sciences (Project 8.14), the Royal Society (RS International Joint Project 2010/R3), the Leverhulme Trust (Project IN-2012-094), the Siberian Branch of the Russian Academy of Sciences (Project 13), the Ministry of Education and Science of the Russian Federation (Project of Joint Laboratories of Siberian Branch of the Russian Academy of Sciences and National Research Universities), and the Russian Foundation for Basic Research (Projects 13-03-00072 and 15-03-03242) for financial support of various parts of this work. N.A.S. thanks the Council for Grants of the President of Russian Federation for postdoctoral scholarship (grant MK-4411.2015.3). B.E.B. is grateful for an EaStCHEM Hirst Academic Fellowship. A.V.Z. thanks the Foundation named after D. I. Mendeleev, Tomsk State University, for support of his work.Low-temperature interaction of [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazole (1) with MoMes2 (Mes = mesitylene / 1,3,5-trimethylbenzene) in tetrahydrofuran gave the heterospin (S1 = S2 = 1/2) radical-ion salt [MoMes2]+[1]– (2) whose structure was confirmed by single-crystal X-ray diffraction (XRD). The structure revealed alternating layers of the cations and anions with the Mes ligands perpendicular, and the anions tilted by 45°, to the layer plane. At 300 K the effective magnetic moment of 2 is equal to 2.40 μB (theoretically expected 2.45 μB) and monotonically decreases with lowering of the temperature. In the temperature range 2−300 K, the molar magnetic susceptibility of 2 is well-described by the Curie-Weiss law with parameters C and θ equal to 0.78 cm3⋅K⋅mol–1 and −31.2 K, respectively. Overall, the magnetic behavior of 2 is similar to that of [CrTol2]+[1]– and [CrCp*2]+[1]–, i.e. changing the cation [MAr2]+ 3d atom M = Cr (Z = 24) with weak spin-orbit coupling (SOC) to a 4d atom M = Mo (Z = 42) with stronger SOC does not affect macroscopic magnetic properties of the salts. For the XRD structure of salt 2, parameters of the Heisenberg spin-Hamiltonian were calculated using the broken-symmetry DFT and CASSCF approaches, and the complex 3D magnetic structure with both the ferromagnetic (FM) and antiferromagnetic (AF) exchange interactions was revealed with the latter as dominating. Salt 2 is thermally unstable and slowly loses the Mes ligands upon storage at ambient temperature. Under the same reaction conditions, interaction of 1 with MoTol2 (Tol = toluene) proceeded with partial loss of the Tol ligands to afford diamagnetic product.PostprintPostprintPeer reviewe

Pressure-induced phenomena in single-walled carbon nanotubes

Pressure-dependent transmittance measurements on films of unoriented and oriented single-walled carbon nanotubes were carried out at room temperature in the midinfrared up to the visible frequency range. The optical transitions in the SWNTs show anomalies at around 2 GPa, which can be attributed to a structural phase transition. The shift to lower frequencies and broadening of the absorption bands with increasing pressure could be attributed to the structural deformation of the SWNTs. We found no indications for a pressure-induced dimensional crossover in the oriented SWNTs