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Fourier transform infrared (FTIR) measurements were carried out on thin films and bulk single crystals of ZnO over a wide temperature range to study the free-carrier and multi-phonon infrared absorptions and the effects of hydrogen incorporation on these properties. Aluminum-doped ZnO thin films were deposited on quartz substrates using atomic-layer deposition (ALD) and sol–gel methods. Hall-effect measurements showed that the ALD films have a resistivity of ρ  = 1.11 × 10 −3  Ω cm, three orders of magnitude lower than sol–gel films ( ρ  = 1.25 Ω cm). This result is consistent with the significant difference in their free-carrier absorption as revealed by FTIR spectra obtained at room temperature. By reducing the temperature to 80 K, the free carriers were frozen out, and their absorption spectrum was suppressed. From the FTIR measurements on ZnO single crystals that were grown by the chemical vapor transport method, we identified a shoulder around 3350 cm −1 and associated it with the presence of two or more hydrogen ions in a Zn vacancy. After reducing the hydrogen level in the crystal, the measurements revealed the multi-phonon absorption of ZnO in the range of 700–1200 cm −1 . This study shows that the multi-phonon absorption bands can be completely masked by the presence of a large concentration of hydrogen in the crystals.

Local vibrational modes can be directly derived from normal vibrational modes using the method of Konkoli and Cremer (Int J Quant Chem 67:29, 1998). This implies the calculation of the harmonic force constant matrix F q (expressed in internal coordinates q ) from the corresponding Cartesian force constant matrix f x with the help of the transformation matrix U  =  WB † ( BWB † ) −1 ( B : Wilson’s B-matrix). It is proven that the local vibrational modes are independent of the choice of the matrix W . However, the choice W  =  M − 1 ( M : mass matrix) has numerical advantages with regard to the choice W  =  I ( I : identity matrix), where the latter is frequently used in spectroscopy. The local vibrational modes can be related to the normal vibrational modes in the form of an adiabatic connection scheme (ACS) after rewriting the Wilson equation with the help of the compliance matrix. The ACSs of benzene and naphthalene based on experimental vibrational frequencies are discussed as nontrivial examples. It is demonstrated that the local-mode stretching force constants provide a quantitative measure for the C–H and C–C bond strength.

We develop a quantum mechanical formalism to treat the strong coupling between an electromagnetic mode and a vibrational excitation of an ensemble of organic molecules. By employing a Bloch-Redfield-Wangsness approach, we show that the influence of dephasing-type interactions, i.e., elastic collisions with a background bath of phonons, critically depends on the nature of the bath modes. In particular, for long-range phonons corresponding to a common bath, the dynamics of the 'bright state' (the collective superposition of molecular vibrations coupling to the cavity mode) is effectively decoupled from other system eigenstates. For the case of independent baths (or short-range phonons), incoherent energy transfer occurs between the bright state and the uncoupled dark states. However, these processes are suppressed when the Rabi splitting is larger than the frequency range of the bath modes, as achieved in a recent experiment (Shalabney et al 2015 Nat. Commun. 6 5981). In both cases, the dynamics can thus be described through a single collective oscillator coupled to a photonic mode, making this system an ideal candidate to explore cavity optomechanics at room temperature.

The translational symmetry of solids, either ordered or disordered, gives rise to the existence of low-frequency phonons. In ordered systems, either crystalline solids or isotropic homogeneous continua, some phonons characterized by different wavevectors are degenerate, i.e. they share the exact same frequency ; in finite-size systems, phonons form a discrete set of bands with nq( )-fold degeneracy. Here we focus on understanding how this degeneracy is lifted in the presence of disorder, and its physical implications. Using standard degenerate perturbation theory and simple statistical considerations, we predict the dependence of the disorder-induced frequency width of phonon bands to be Δ ∼ n q N , where is the strength of disorder and N is the total number of particles. This theoretical prediction is supported by extensive numerical calculations for disordered lattices-characterized by topological, mass, stiffness and positional disorder-and for computer glasses, where disorder is self-generated, thus establishing its universal nature. The predicted scaling of phonon band widths leads to the identification of a crossover frequency † ∼ L − 2 ( + 2 ) in systems of linear size L in > 2 dimensions, where the disorder-induced width of phonon bands becomes comparable to the frequency gap between neighboring bands. Consequently, phonons continuously cover the frequency range > †, where the notion of discrete phonon bands becomes ill-defined. Two basic applications of the theory are presented; first, we show that the phonon scattering lifetime is proportional to (Δ )−1 for < †. Second, the theory is applied to the basic physics of glasses, allowing us to determine the range of frequencies in which the recently established universal density of states of non-phononic excitations can be directly probed for different system sizes.

The effect of Zn-doping in CoFe 2 O 4 nanoparticles (NPs) through chemical co-precipitation route was investigated in term of structural, optical, and magnetic properties. Both XRD and FTIR analyses confirm the formation of cubic spinel phase, where the crystallite size changes with Zn content from 46 to 77 nm. The Scherrer method, Williamson-Hall (W-H) analysis, and size-strain plot method (SSPM) were used to study of crystallite sizes. The TEM results were in good agreement with the results of the SSP method. SEM observations reveal agglomeration of fine spherical-like particles. The optical band gap energy determined from diffuse reflectance spectroscopy (DRS) varies increases from 1.17 to 1.3 eV. Magnetization field loops reveal a ferromagnetic behavior with lower hysteresis loop for higher Zn content. The magnetic properties are remarkably influenced with Zn doping; saturation magnetization (M s ) increases then decreases while both coercivity (H C ) and remanent magnetization (M r ) decrease continuously, which was associated with preferential site occupancy and the change in particle size.

Over the past two decades, the vibrational Stark effect has become an important tool to measure and analyze the in situ electric field strength in various chemical environments with infrared spectroscopy. The underlying assumption of this effect is that the normal stretching mode of a target bond such as CO or CN of a reporter molecule (termed vibrational Stark effect probe) is localized and free from mass-coupling from other internal coordinates, so that its frequency shift directly reflects the influence of the vicinal electric field. However, the validity of this essential assumption has never been assessed. Given the fact that normal modes are generally delocalized because of mass-coupling, this analysis was overdue. Therefore, we carried out a comprehensive evaluation of 68 vibrational Stark effect probes and candidates to quantify the degree to which their target normal vibration of probe bond stretching is decoupled from local vibrations driven by other internal coordinates. The unique tool we used is the local mode analysis originally introduced by Konkoli and Cremer, in particular the decomposition of normal modes into local mode contributions. Based on our results, we recommend 31 polyatomic molecules with localized target bonds as ideal vibrational Stark effect probe candidates.

This review summarizes the recent developments regarding the use of uranium as nuclear fuel, including recycling and health aspects, elucidated from a chemical point of view, i.e., emphasizing the rich uranium coordination chemistry, which has also raised interest in using uranium compounds in synthesis and catalysis. A number of novel uranium coordination features are addressed, such the emerging number of U(II) complexes and uranium nitride complexes as a promising class of materials for more efficient and safer nuclear fuels. The current discussion about uranium triple bonds is addressed by quantum chemical investigations using local vibrational mode force constants as quantitative bond strength descriptors based on vibrational spectroscopy. The local mode analysis of selected uranium nitrides, N≡U≡N, U≡N, N≡U=NH and N≡U=O, could confirm and quantify, for the first time, that these molecules exhibit a UN triple bond as hypothesized in the literature. We hope that this review will inspire the community interested in uranium chemistry and will serve as an incubator for fruitful collaborations between theory and experimentation in exploring the wealth of uranium chemistry.

Solvation of molecules in water is at the heart of a myriad of molecular phenomena and of crucial importance to understanding such diverse issues as chemical reactivity or biomolecular function. Complementing well-established approaches, it has been shown that laser spectroscopy in the THz frequency domain offers new insights into hydration from small solutes to proteins. Upon introducing spatially-resolved analyses of the absorption cross section by simulations, the sensitivity of THz spectroscopy is traced back to characteristic distance-dependent modulations of absorption intensities for bulk water. The prominent peak at≈200 cm⁻¹ is dominated by first-shell dynamics, whereas a concerted motion involving the second solvation shell contributes most significantly to the absorption at about 80 cm⁻¹ ≈2.4 THz. The latter can be understood in terms of an umbrella-like motion of two hydrogen-bonded tetrahedra along the connecting hydrogen bond axis. Thus, a modification of the hydrogen bond network, e.g., due to the presence of a solute, is expected to affect vibrational motion and THz absorption intensity at least on a length scale that corresponds to two layers of solvating water molecules. This result provides a molecular mechanism explaining the experimentally determined sensitivity of absorption changes in the THz domain in terms of distinct, solute-induced dynamical properties in solvation shells of (bio)molecules—even in the absence of well-defined resonances.

A 'protein quake' is directly monitored on the picosecond timescale using the method of time-resolved wide-angle X-ray scattering at an X-ray free-electron laser. We describe a method to measure ultrafast protein structural changes using time-resolved wide-angle X-ray scattering at an X-ray free-electron laser. We demonstrated this approach using multiphoton excitation of the Blastochloris viridis photosynthetic reaction center, observing an ultrafast global conformational change that arises within picoseconds and precedes the propagation of heat through the protein. This provides direct structural evidence for a 'protein quake': the hypothesis that proteins rapidly dissipate energy through quake-like structural motions.

We present a model of a mechanical system with a vibrational mode spectrum identical to the spectrum of electronic excitations in a tight-binding model of graphene. The model consists of point masses connected by elastic couplings, called 'tri-bonds', that implement certain three-body interactions, which can be tuned by varying parameters that correspond to the relative hopping amplitudes on the different bond directions in graphene. In the mechanical model, this is accomplished by varying the location of a pivot point that determines the allowed rigid rotations of a single tri-bond. The infinite system constitutes a Maxwell lattice, with the number of degrees of freedom equal to the number of constraints imposed by the tri-bonds. We construct the equilibrium and compatibility matrices and analyze the model's phase diagram, which includes spectra with Weyl points for some placements of the pivot and topologically polarized phases for others. We then discuss the edge modes and associated states of self stress for strips cut from the periodic lattice. Finally, we suggest a physical realization of the tri-bond, which allows access to parameter regimes not available to experiments on (strained) graphene and may be used to create other two-dimensional mechanical metamaterials with different spectral features.