Conformational Characterization of S-Methyl Dithiocarbazate by Infrared Spectra and Vibrational Assignments

Infrared spectra are recorded for S-methyl dithiocarbazate and its N-deuterated compound in two molecular conformations in the solid state and in solution between 4000 and 30 cm−1. The assignments have been supported from a complete normal coordinate analysis; the conformation sensitive bands of the –CSNHNH2 grouping are discussed. The assignments are compared with those of related molecules to check the internal consistency and to obtain the pattern of the characteristic bands of thiocarbazoyl (–CSNHNH2) group. The magnitudes of the C–N and S–CH3 torsional barriers are estimated from the force constants.

Spectral Sensing for Cognitive Radio: Estimation of Adaptive Frequency Hopping Signal

The issue of dynamic spectrum scene analysis in any cognitive radio network becomes extremely complex when low probability of intercept, spread spectrum systems are present in environment. The detection and estimation become more complex if frequency hopping spread spectrum is adaptive in nature. In this paper, we propose two phase approach for detection and estimation of frequency hoping signals. Polyphase filter bank has been proposed as the architecture of choice for detection phase to efficiently detect the presence of frequency hopping signal. Based on the modeling of frequency hopping signal it can be shown that parametric methods of line spectral analysis are well suited for estimation of frequency hopping signals if the issues of order estimation and time localization are resolved. An algorithm using line spectra parameter estimation and wavelet based transient detection has been proposed which resolves above issues in computationally efficient manner suitable for implementation in cognitive radio. The simulations show promising results proving that adaptive frequency hopping signals can be detected and demodulated in a non cooperative context, even at a very low signal to noise ratio in real time.

Complexes of lanthanide nitrates with 2-N-(6-picoIyl)-benzamide

New complexes of lanthanide nitrates with 2-N-(6-picolyl)-benzamide of the formulae Ln2[6-pic-BA], [NO3l6 (Ln = Y and La-Yb) have been prepared and characterised by chemical analysis, infrared, molar conductance and electronic spectral data. Molar conductance data along with IR data point to the presence of co-ordinated nitrate groups. IR spectra prove the bidentate co-ordination of the ligand to the metal ion, through the oxygen of the secondary amide and the nitrogen of the heterocyclic ring. Electronic spectral studies in the visible region suggest an eight co-ordinate geometry around the metal ions.

Estimation of peak ground acceleration and spectral acceleration for South India with local site effects: probabilistic approach

In this work an attempt has been made to evaluate the seismic hazard of South India (8.0 degrees N-20 degrees N; 72 degrees E-88 degrees E) based on the probabilistic seismic hazard analysis (PSHA). The earthquake data obtained from different sources were declustered to remove the dependent events. A total of 598 earthquakes of moment magnitude 4 and above were obtained from the study area after declustering, and were considered for further hazard analysis. The seismotectonic map of the study area was prepared by considering the faults, lineaments and the shear zones in the study area which are associated with earthquakes of magnitude 4 and above. For assessing theseismic hazard, the study area was divided into small grids of size 0.1 degrees x0.1 degrees, and the hazard parameters were calculated at the centre of each of these grid cells by considering all the seismic sources with in a radius of 300 km. Rock level peak horizontal acceleration (PHA) and spectral acceleration (SA) values at 1 corresponding to 10% and 2% probability of exceedance in 50 years have been calculated for all the grid points. The contour maps showing the spatial variation of these values are presented here. Uniform hazard response spectrum (UHRS) at rock level for 5% damping and 10% and 2% probability of exceedance in 50 years were also developed for all the grid points. The peak ground acceleration (PGA) at surface level was calculated for the entire South India for four different site classes. These values can be used to find the PGA values at any site in South India based on site class at that location. Thus, this method can be viewed as a simplified method to evaluate the PGA values at any site in the study area.

How Good is the Assumption About Visible Surface Reflectance in MODIS Aerosol Retrieval Over Land? A Comparison With Aircraft Measurements Over an Urban Site in India

In this paper, we discuss the measurements of spectral surface reflectance (rho(s)(lambda)) in the wavelength range 350-2500 nm measured using a spectroradiometer onboard a low-flying aircraft over Bangalore (12.95 degrees N, 77.65 degrees E), an urban site in southern India. The large discrepancies in the retrieval of aerosol propertiesover land by the Moderate-Resolution Imaging Spectroradiometer (MODIS), which could be attributed to the inaccurate estimation of surface reflectance at many sites in India and elsewhere, provided motivation for this paper. The aim of this paper was to verify the surface reflectance relationships assumed by the MODIS aerosol algorithm for the estimation of surface reflectance in the visible channels (470 and 660 nm) from the surface reflectance at 2100 nm for aerosol retrieval over land. The variety of surfaces observed in this paper includes green and dry vegetations, bare land, and urban surfaces. The measuredreflectance data were first corrected for the radiative effects of atmosphere lying between the ground and aircraft using the Second Simulation of Satellite Signal in the Solar Spectrum (6S) radiative transfer code. The corrected surface reflectance in the MODIS's blue (rho(s)(470)), red (rho(s)(660)), and shortwave-infrared (SWIR) channel (rho(s)(2100)) was linearly correlated. We found that the slope of reflectance relationship between 660 and 2100 nm derived from the forward scattering data was 0.53 with an intercept of 0.07, whereas the slope for the relationship between the reflectance at 470 and 660 nm was 0.85. These values are much higher than the slope (similar to 0.49) for either wavelengths assumed by the MODIS aerosol algorithm over this region. The reflectance relationship for the backward scattering data has a slope of 0.39, with an intercept of 0.08 for 660 nm, and 0.65, with an intercept of 0.08 for 470 nm. The large values of the intercept (which is very small in the MODIS reflectance relationships) result in larger values of absolute surface reflectance in the visible channels. The discrepancy between the measured and assumed surface reflectances could lead to error in the aerosol retrieval. The reflectance ratio (rho(s)(660)/rho(s)(2100)) showed a clear dependence on the N D V I-SWIR where the ratio increased from 0.5 to 1 with an increase in N V I-SWIR from 0 to 0.5. The high correlation between the reflectance at SWIR wavelengths (2100, 1640, and 1240 nm) indicated an opportunity to derive the surface reflectance and, possibly, aerosol properties at these wavelengths. We need more experiments to characterize the surface reflectance and associated inhomogeneity of land surfaces, which play a critical role in the remote sensing of aerosols over land.

Raman and polarized infrared spectra of pyridine-2-thione

Polarized i.r. spectra of oriented polycrystals and the i.r. and Raman spectra of polycrystalline samples of pyridine-2-thione have been obtained. The Raman spectra of a solution of pyridine-2-thione has also been measured and the polarization of many lines determined. The i.r. spectra of S-methyl and N-deuterated compounds have also been investigated. A complete assignment of all the observed peaks has been possible. The results are correlated with the assignments available for related systems.

Complexes of Lanthanide Perchlorates with N-(2-Pyrimidyl)benzamide

New complexes of lanthanide perchlorates with N-(2-pyrimidyl)benzamide (BApymH) of the general formulae [Ln(BApymH)4](ClO4)3 (where Ln = La-Yb and Y) have been synthesised and characterised by chemical analysis, molar conductivity and physical methods such as infrared and electronic spectra in the visible region. Molar conductance and infrared data point to the ionic nature of the per-chlorate groups in the complexes. IR data unequivocally proves that the coordination of the ligand to the metal ion takes place in a bidentate fashion through the oxygen of the secondary amide and nitrogen of the pyrimidine ring. From a comparison of the visible electronic spectral shapes of the Nd3+ and Ho3+ complexes with those reported in the literature, an eight coordinate geometry around the metal ion has tentatively been assigned in all the complexes.

Spectral analysis of finite section normal integral operators

Some continuity and differentiability properties of the eigenvalues and eigenfunctions of finite section normal integral operators are proved. These are the extension of corresponding results for symmetric operators ([4.], 554–566; K. B. Athreya and R. Vittal Rao, to appear; [10.], 463–471.

Infrared spectra of 1.3-dithiole-2-thione and its selenium analogues ând frequency assignment and molecular force constants

Infrared spectra of 1,3-dithiole-2-thione (DTT) and its four selenium analogues have been studied in the region 4000 to 20 cm�1. Assignment of all the fundamental frequencies was made by noting the band shifts on progressive selenation. Normal coordinate analysis procedures have been applied for both in-plane and out-of-plane vibrations to help the assignments. The Urey�Bradley force function supplemented with valence force constants for the out-of-plane vibrations was employed for coordinate calculations. A correlation of the infrared assignments of DTT with its different selenium analogues is accomplished. Further, the infrared assignments are compared with those of trithiocarbonate ion and its selenium analogues and other structurally related heterocyclic molecules.

1H and 13C NMR spectral studies of C-2 substituted isomeric exo- and endo-5-methyl-bicyclo[3.2.1]octane-6,8-diones

A detailed analysis of the 1H and 13C NMR spectra of C-2 aryl and alkyl/desalkyl substituted isomeric exo- and endo-5-methylbicyclo[3.2.1]octane-6,8-diones is presented. The chemical shift of the C-5 angular methyl, the C-2 alkyl/olefinic (C-10)/C-2 methine protons, the aromatic proton shieldings and the characteristic AMX and ABX spectral pattern of the ketomethylene and bridgehead protons were found to be sensitive to the phenyl ring orientation (anisotropy). These distinctive features could be used for configurational distinction for this class of compounds. With increasing ortho-methoxy substitution on the phenyl ring, considerable deshilelding of the bridgehead proton was observed (ca. 0.6 ppm). Absence of the C-2 alkyl group in the desalkyl isomers resulted in substantial changes in the chemical shifts of different protons. A study of the NMR spectra of the corresponding bicyclic compounds with C-2 methoxy/hydroxy substitution instead of the aryl group revealed that the anisotropy of the phenyl ring and the electronegative oxygen substituents have opposite effects. The 13C NMR spectral assignment of each carbon resonance of C-2 aryl and alkyl/desalkyl substituted isomeric exo- and endo-5-methylbicyclo[3.2.1]octane-6,8-diones and the corresponding C-2 methoxy/hydroxy/chloro and methyl bicyclic compounds are reported. Additional ortho-methoxy substitution on the phenyl ring was found to produce considerable high field shifts of the C-10 and C-1 carbon resonances. A high-field shift was observed for the C-6 and C-8 carbonyl carbons, presumably due to 1,3-dicarbonyl interactions. The chemical shifts of C-1 aromatic, C-10 alkyl and C-2 carbons, which are sensitive to exo/endo isomerism, could be utilized in differentiating a pair of isomers.

Infrared and Mössbauer spectroscopic study of the metal-insulator transition in some oxides of perovskite structure

The IR spectra of some LaNi1−xBxO3 (B = Cr, Fe, and Co) compounds having perovskite structure have been studied in the range 1000−300 cm−1. An investigation of the changes in the metal-oxygen stretching frequency as x → xc from the insulating side has been carried out. An important feature is that as x → xc the vibrational features in the infrared spectra disappear when the resistivity is not, vert, similar10−1 Ω cm which is of two orders of magnitude more than the value of varrho0 at which the temperature coefficient of resistance changes sign. Mössbauer studies on Fe-containing samples with various conductivities show that the isomer shift decreases as conductivity increases which is indicative of larger Fe---O overlap.

Short-window spectral analysis using AMVAR and multitaper methods: a comparison

We compare two popular methods for estimating the power spectrum from short data windows, namely the adaptive multivariate autoregressive (AMVAR) method and the multitaper method. By analyzing a simulated signal (embedded in a background Ornstein-Uhlenbeck noise process) we demonstrate that the AMVAR method performs better at detecting short bursts of oscillations compared to the multitaper method. However, both methods are immune to jitter in the temporal location of the signal. We also show that coherence can still be detected in noisy bivariate time series data by the AMVAR method even if the individual power spectra fail to show any peaks. Finally, using data from two monkeys performing a visuomotor pattern discrimination task, we demonstrate that the AMVAR method is better able to determine the termination of the beta oscillations when compared to the multitaper method.

Mechanistic studies on the action of ammonium phosphate on polymer fire retardancy

The mechanism of fire retardant action of mono- and diammonium phosphates on polystyrene has been investigated. Ignition delay and mass burning rate studies reveal that the phosphates bring down both parameters considerably though to different extents. This has been adequately explained on the basis of the existing combustion models and physicochemical behavior of the material. Similar to their action on cellulosic materials, phosphates bring about fire retardancy in polystyrene via char formation. This is suggested to occur through a series of processes consisting of initial peroxide formation, decomposition to alcohols and aldehydes, formation of alkyl-phosphate esters, dehydration and subsequent char formation. Infrared and mass spectral studies support this mechanism.

Infrared spectra of some oxides of K2NiF4 and related structures

The i.r. spectra of some Ln2BO4 and LnSrBO4 compounds (Ln = La, Pr, Nd, Sm or Gd;B = Fe, Al, Co or Cu) with K2NiF4 or related structures have been studied in the range 800-300 cm−1. The BO6 octahedra in compounds with K2NiF4 structure are elongated. The assignment of the bands in terms of internal modes of sheets of bridged BO6 octahedra or square-planar BO4 sheets has been considered. The observed spectra are correlated with those of solid solutions of these oxides and of LnBO3 perovskites. Unusually high stretching frequencies found in some of the oxides are discussed in terms of the short B---O bonds in the basal plane and the Ln---O bonds along the c axis.