A Raman spectroscopic study of the low-frequency vibrations of o-dimethoxybenzene and its methyl deuterated analogues

The low-frequency (100–400 cm⁻¹) Raman spectra of liquid (at 300 K) and solid (at 130 K) veratrole (o-dimethoxybenzene), and its methyl deuterated analogues, have been measured. The methyl and methoxyl torsional transitions have been identified, and the corresponding rotational barriers have been determined. The interpretation of the spectra points to a conformationally mixed situation for solid veratrole, in which both planar and non-planar conformers may co-exist.     

Subcritical scattering from buried elastic shells

Buried objects have been largely undetectable by traditional high-frequency sonars due to their insignificant bottom penetration. Further, even a high grazing angle sonar approach is vastly limited by the coverage rate dictated by the finite water depth, making the detection and classification of buried objects using low frequency, subcritical sonar an interesting alternative. On the other hand, such a concept would require classification clues different from the traditional high-resolution imaging and shadows to maintain low false alarm rates. A potential alternative, even for buried targets, is classification based on the acoustic signatures of man-made elastic targets. However, the elastic responses of buried and proud targets are significantly different. The objective of this work is to identify, analyze, and explain some of the effects of the sediment and the proximity of the seabed interface on the scattering of sound from completely and partially buried elastic shells. The analysis was performed using focused array processing of data from the GOATS98 experiment carried out jointly by MIT and SACLANTCEN, and a new hybrid modeling capability combining a virtual source-or wave-field superposition-approach with an exact spectral integral representation of the Green's functions for a stratified ocean waveguide, incorporating all multiple scattering between the object and the seabed. Among the principal results is the demonstration of the significant role of structural circumferential waves in converting incident, evanescent waves into backscattered body waves, emanating to the receivers at supercritical grazing angles, in effect making the target appear closer to the sonar than predicted by traditional ray theory.     

Mechanism for NO2 charging on metal supported MgO

NO2 adsorbed on MgO(100) supported by Ag or Pt is explored by density functional theory calculations. NO2 is weakly adsorbed on MgO(100), with a bond involving minor oxide to adsorbate charge transfer. However, if MgO is supported, then the adsorption energy is considerably enhanced and NO2 is adsorbed as a nitrite (N). Analysis reveals that the NO2 excess charge originates from the oxide side of the oxide/metal interface and that the electron abstraction increases the oxide/metal adhesion. The proposed mechanism is general and should apply for oxidizing surface species.     

OH-stretch vibrational spectroscopy of hydroxymethyl hydroperoxide

We report measurement and analysis of the photodissociation spectrum of hydroxymethyl hydroperoxide (HOCH(2)OOH) and its partially deuterated analogue, HOCD(2)OOH, in the OH-stretching region. Spectra are obtained by Fourier transform infrared spectroscopy in the 1nu(OH) and 2nu(OH) regions, and by laser induced fluorescence detection of the OH fragment produced from dissociation of HOCH(2)OOH initiated by excitation of the 4nu(OH) and 5nu(OH) overtone regions (action spectroscopy). A one-dimensional local-mode model of each OH chromophore is used with ab initio calculated OH-stretching potential energy and dipole moment curves at the coupled-cluster level of theory. Major features in the observed absorption and photodissociation spectra are explained by our local-mode model. In the 4nu(OH) region, explanation of the photodissocation spectrum requires a nonuniform quantum yield, which is estimated by assuming statistical energy distribution in the excited state. Based on the estimated dissociation threshold, overtone photodissociation is not expected to significantly influence the atmospheric lifetime of hydroxymethyl hydroperoxide.     

Photodissociation of formyl fluoride in rare gas matrixes

Photodissociation of formyl fluoride (HCOF) is studied in Ar, Kr, and Xe matrixes at 248 and 193 nm excitation by following spectral changes in the infrared absorption spectra. In all matrixes, the main photodissociation products are CO/HF species, including CO-HF and OC-HF complexes and thermally unstable CO/HF species (a distorted CO/HF complex or a reaction intermediate), which indicate negligible cage exit of atoms produced via the C-F and C-H bond cleavage channels. However, the observation of traces of H, F, CO, CO(2), F(2)CO, FCO, and HRg(2)(+) (Rg = Kr or Xe) in Kr and Xe matrixes would imply some importance of other reaction channels too. The analysis of the decay curves of the precursor shows that dissociation efficiency of HCOF increases as Ar < Kr < Xe, the difference being the factor of 10 between Ar and Xe. Moreover, HCOF dissociates 20-50 times faster at 193 nm compared to 248 nm. Interestingly, whereas the CO/HF species are stable with respect to photolysis in Ar, they photobleach in Kr and Xe matrixes at 248 and 193 nm, even though the first excited states of CO and HF are not energetically accessible with 193 and 248 nm photons. In krypton matrix, the photodissociation of CO/HF species at 248 nm is observed to be a single photon process. Quantum chemical calculations of electronic excitation energies of CO-HF and OC-HF complexes show that the electronic states of HF and CO mostly retain their diatomic nature in the pair. This clearly demonstrates that photodissociation of CO/HF complexes is promoted by the surrounding rare gas lattice.     

Three-Dimensional Mode Coupling around a Conical Seamount and the Use of Random Discretization

Three-dimensional mode coupling around a conical seamount in an ocean waveguide is studied. It is shown that strong mode coupling occurs at the edge of a conical seamount for the incident normal modes with significant amplitudes below the top of the seamount. Therefore, mode coupling is critical for the investigation of the acoustic field around a seamount. In addition, we suggest the use of random discretization for representing smoothly varying bathymetry. For the use of uniform discretization, when the horizontal step size is greater than half of the wavelength, artificial diffraction lobes appear due to coherent backscatter. However, by using the random discretization scheme instead, such artificial diffraction lobes are diffused, resulting in a faster convergence rate.     

Subpicosecond hard x-ray streak camera using single-photon counting

We have developed and characterized a hard x-ray accumulating streak camera that achieves subpicosecond time resolution by using single-photon counting. A high repetition rate of 2 kHz was achieved by use of a readout camera with built-in image processing capabilities. The effects of sweep jitter were removed by using a UV timing reference. The use of single-photon counting allows the camera to reach a high quantum efficiency by not limiting the divergence of the photoelectrons.     

Ecosystems perspective on financial networks: Diagnostic tools

The world economy consists of highly interconnected and interdependent commercial and financial networks. Here, we develop temporal and structural network tools to analyze the state of the economy and the financial markets. Our analysis indicates that a strong clustering can be a warning sign. Reduction in diversity, which was an essential aspect of the dynamics surrounding the financial markets crisis of 2008, is seen as a key emergent feature arising naturally from the evolutionary and adaptive dynamics inherent to the financial markets. Similarly, collusion amongst construction firms in a number of regions in Japan in the 2000s can be identified with the formation of clusters of anomalous highly connected companies. © 2013 Wiley Periodicals, Inc. Complexity 19: 22–36, 2013     

Entangled economy: An ecosystems approach to modeling systemic level dynamics

We present a model of an economy inspired by individual based model approaches in evolutionary ecology. We demonstrate that evolutionary dynamics in a space of companies interconnected through a correlated interaction matrix produces time dependencies of the total size of the economy, total number of companies, companies’ age and capital distribution that compares well with statistics for the USA. We discuss the relevance of our modeling framework to policy making.