Conformational transitions of glycine induced by vibrational excitation of the O-H stretch

Vibrational energy flow and conformational transitions following excitation of the OH stretching mode of the most stable conformer of glycine are studied by classical trajectories. "On the fly" simulations with the PM3 semiempirical electronic structure method for the potential surface are used. Initial conditions are selected to correspond to the v = 1 excitation of the OH stretch. The main findings are: (1) An an equilibrium-like ratio is established between the populations of the 3 lowest-lying conformers after about 10 picoseconds. (2) There is a high probability throughout the 150 ps of the simulations for finding the molecule in geometries far from the equilibrium structures of the lowest-energy conformers. (3) Energy from the initial excited OH (v = 1) stretch flows preferentially to 5 other vibrational modes, including the bending motion of the H atom. (4) RRK theory yields conformational transition rates that deviate substantially from the classical trajectory results. Possible implication of these results for vibrational energy flow and conformational transitions in small biological molecules are discussed.

Dual-energy multidetector CT: how does it work, what can it tell us, and when can we use it in abdominopelvic imaging?

Dual-energy CT provides information about how substances behave at different energies, the ability to generate virtual unenhanced datasets, and improved detection of iodine-containing substances on low-energy images. Knowing how a substance behaves at two different energies can provide information about tissue composition beyond that obtainable with single-energy techniques. The term K edge refers to the spike in attenuation that occurs at energy levels just greater than that of the K-shell binding because of the increased photoelectric absorption at these energy levels. K-edge values vary for each element, and they increase as the atomic number increases. The energy dependence of the photoelectric effect and the variability of K edges form the basis of dual-energy techniques, which may be used to detect substances such as iodine, calcium, and uric acid crystals. The closer the energy level used in imaging is to the K edge of a substance such as iodine, the more the substance attenuates. In the abdomen and pelvis, dual-energy CT may be used in the liver to increase conspicuity of hypervascular lesions; in the kidneys, to distinguish hyperattenuating cysts from enhancing renal masses and to characterize renal stone composition; in the adrenal glands, to characterize adrenal nodules; and in the pancreas, to differentiate between normal and abnormal parenchyma.

The Role of Anharmonicity in Hydrogen-Bonded Systems: The Case of Water Clusters

The nature of vibrational anharmonicity has been examined for the case of small water clusters using second-order vibrational perturbation theory (VPT2) applied on second-order Møller–Plesset perturbation theory (MP2) potential energy surfaces. Using a training set of 16 water clusters (H2O)n=2–6,8,9 with a total of 723 vibrational modes, we determined scaling factors that map the harmonic frequencies onto anharmonic ones. The intermolecular modes were found to be substantially more anharmonic than intramolecular bending and stretching modes. Due to the varying levels of anharmonicity of the intermolecular and intramolecular modes, different frequency scaling factors for each region were necessary to achieve the highest accuracy. Furthermore, new scaling factors for zero-point vibrational energies (ZPVE) and vibrational corrections to the enthalpy (ΔHvib) and the entropy (Svib) have been determined. All the scaling factors reported in this study are different from previous works in that they are intended for hydrogen-bonded systems, while others were built using experimental frequencies of covalently bonded systems. An application of our scaling factors to the vibrational frequencies of water dimer and thermodynamic functions of 11 larger water clusters highlights the importance of anharmonic effects in hydrogen-bonded systems.

Simulating Energy Transfer and Upconversion in β-NaYF 4 : Yb 3+ , Tm 3+

The design of upconversion phosphors with higher quantum yield requires a deeper understanding of the detailed energy transfer and upconversion processes between active ions inside the material. Rate equations can model those processes by describing the populations of the energy levels of the ions as a function of time. However, this model presents some drawbacks: energy migration is assumed to be infinitely fast, it does not determine the detailed interaction mechanism (multipolar or exchange), and it only provides the macroscopic averaged parameters of interaction. Hence, a rate equation model with the same parameters cannot correctly predict the time evolution of upconverted emission and power dependence under a wide range of concentrations of active ions. We present a model that combines information about the host material lattice, the concentration of active ions, and a microscopic rate equation system. The extent of energy migration is correctly taken into account because the energy transfer processes are described on the level of the individual ions. This model predicts the decay curves, concentration, and excitation power dependences of the emission. This detailed information can be used to predict the optimal concentration that results in the maximum upconverted emission.

Theoretical Transition Probabilities, Oscillator Strengths and Radiative Lifetimes Of Levels In Pb IV

Transitionprobabilities and oscillatorstrengths of 176 spectral lines with astrophysical interest arising from 5d10ns (n = 7,8), 5d10np (n = 6,7), 5d10nd (n = 6,7), 5d105f, 5d105g, 5d10nh (n = 6,7,8), 5d96s2, and 5d96s6p configurations, and radiativelifetimes for 43 levels of PbIV, have been calculated. These values were obtained in intermediate coupling (IC) and using relativistic Hartree–Fock calculations including core-polarization effects. For the IC calculations, we use the standard method of least-square fitting from experimental energy levels by means of the Cowan computer code. The inclusion in these calculations of the 5d107p and 5d105f configurations has facilitated a complete assignment of the energy levels in the PbIV. Transitionprobabilities, oscillatorstrengths, and radiativelifetimes obtained are generally in good agreement with the experimental data.

Deep levels in a-plane, high Mg-content MgxZn1-xO epitaxial layers grown by molecular beam epitaxy

Deep level defects in n-type unintentionally doped a-plane MgxZn1−xO, grown by molecular beam epitaxy on r-plane sapphire were fully characterized using deep level optical spectroscopy (DLOS) and related methods. Four compositions of MgxZn1−xO were examined with x = 0.31, 0.44, 0.52, and 0.56 together with a control ZnO sample. DLOS measurements revealed the presence of five deep levels in each Mg-containing sample, having energy levels of Ec − 1.4 eV, 2.1 eV, 2.6 V, and Ev + 0.3 eV and 0.6 eV. For all Mg compositions, the activation energies of the first three states were constant with respect to the conduction band edge, whereas the latter two revealed constant activation energies with respect to the valence band edge. In contrast to the ternary materials, only three levels, at Ec − 2.1 eV, Ev + 0.3 eV, and 0.6 eV, were observed for the ZnO control sample in this systematically grown series of samples. Substantially higher concentrations of the deep levels at Ev + 0.3 eV and Ec − 2.1 eV were observed in ZnO compared to the Mg alloyed samples. Moreover, there is a general invariance of trap concentration of the Ev + 0.3 eV and 0.6 eV levels on Mg content, while at least and order of magnitude dependency of the Ec − 1.4 eV and Ec − 2.6 eV levels in Mg alloyed samples.

Vibrational population relaxation of carbon monoxide in the heme pocket of photolyzed carbonmonoxy myoglobin: Comparison of time-resolved mid-IR absorbance experiments and molecular dynamics simulations

The vibrational energy relaxation of carbon monoxide in the heme pocket of sperm whale myoglobin was studied by using molecular dynamics simulation and normal mode analysis methods. Molecular dynamics trajectories of solvated myoglobin were run at 300 K for both the δ- and ɛ-tautomers of the distal His-64. Vibrational population relaxation times of 335 ± 115 ps for the δ-tautomer and 640 ± 185 ps for the ɛ-tautomer were estimated by using the Landau–Teller model. Normal mode analysis was used to identify those protein residues that act as the primary “doorway” modes in the vibrational relaxation of the oscillator. Although the CO relaxation rates in both the ɛ- and δ-tautomers are similar in magnitude, the simulations predict that the vibrational relaxation of the CO is faster in the δ-tautomer with the distal His playing an important role in the energy relaxation mechanism. Time-resolved mid-IR absorbance measurements were performed on photolyzed carbonmonoxy hemoglobin (Hb13CO). From these measurements, a T1 time of 600 ± 150 ps was determined. The simulation and experimental estimates are compared and discussed.

Vibrational methods applied to NDT testing and fluid density measurement

A system for the NDI' testing of the integrity of conposite materials and of adhesive bonds has been developed to meet industrial requirements. The vibration techniques used were found to be applicable to the development of fluid measuring transducers. The vibrational spectra of thin rectangular bars were used for the NDT work. A machined cut in a bar had a significant effect on the spectrum but a genuine crack gave an unambiguous response at high amplitudes. This was the generation of fretting crack noise at frequencies far above that of the drive. A specially designed vibrational decrement meter which, in effect, measures mechanical energy loss enabled a numerical classification of material adhesion to be obtained. This was used to study bars which had been flame or plasma sprayed with a variety of materials. It has become a useful tool in optimising coating methods. A direct industrial application was to classify piston rings of high performance I.C. engines. Each consists of a cast iron ring with a channel into which molybdenum, a good bearing surface, is sprayed. The NDT classification agreed quite well with the destructive test normally used. The techniques and equipment used for the NOT work were applied to the development of the tuning fork transducers investigated by Hassan into commercial density and viscosity devices. Using narrowly spaced, large area tines a thin lamina of fluid is trapped between them. It stores a large fraction of the vibrational energy which, acting as an inertia load reduces the frequency. Magnetostrictive and piezoelectric effects together or in combination enable the fork to be operated through a flange. This allows it to be used in pipeline or 'dipstick' applications. Using a different tine geometry the viscosity loading can be predoninant. This as well as the signal decrement of the density transducer makes a practical viscometer.

Energy level decay and excited state absorption processes in erbium-doped tellurium glass

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Energy level decay and excited state absorption processes in dysprosium-doped fluoride glass

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Energy transfer rates and population inversion of sup(4)Isub(11/2) excited state of Ersup(3+) investigated by means of numerical solutions of the rate equations system in Er:LiYFsub(4) crystal

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Energy transfer and energy level decay processes in Tmsup(3+)-doped tellurite glass

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)