Adsorption of carbon monoxide on the surfaces of polycrystalline transition metals and alloys: electron energy loss and ultraviolet photoelectron spectral studies1

Adsorption of CO has been investigated on the surfaces of polycrystalline transition metals as well as alloys by employing electron energy loss spectroscopy (eels) and ultraviolet photoelectron spectroscopy (ups). CO adsorbs on polycrystalline transition metal surfaces with a multiplicity of sites, each being associated with a characteristic CO stretching frequency; the relative intensities vary with temperature as well as coverage. Whilst at low temperatures (80- 120 K), low coordination sites are stabilized, the higher coordination sites are stabilized at higher temperatures (270-300 K). Adsorption on surfaces of polycrystalline alloys gives characteristic stretching frequencies due to the constituent metal sites. Alloying, however, causes a shift in the stretching frequencies, indicating the effect of the band structure on the nature of adsorption. The up spectra provide confirmatory evidence for the existence of separate metal sites in the alloys as well as for the high-temperature and low-temperature phases of adsorbed CO.

Vibrational assignments of five-membered heterocyclic compounds. Normal vibrations of oxazolidine-2-one and -2-thione

Infrared spectra of oxazolidine-2-one (Oxo), -2-thione (Oxt) and their N-deuteriated derivatives have been measured over the range 4000-20 cm−1. The fundamental frequencies of these molecules have been assigned on the basis of normal coordinate calculations carried out using a Urey-Bradley potential function supplemented with valence type constants for the out-of-plane modes of the planar skeleton. The results of the vibrational analyses are discussed and correlated with the assignments available for the other related five membered heterocyclic molecules.

Spectroscopic and Coordination Behavior of α-Cyanothioacetamide

α-Cyanothioacetamide (CTAM) complexes of cuprous chloride CuCl–2CTAM and cuprous bromide CuBr–2CTAM have been prepared. The infrared spectra of CTAM and its complexes, and the laser Raman spectrum of CTAM have been recorded. Assignment of the frequencies of the ligand has been made on the basis of a normal coordinate analysis using the Urey-Bradley force field. The copper (I) complexes are inferred to have thiocarbonyl sulfur and amide nitrogen bonded CTAM as evidenced from infrared and electronic spectra.

Infrared spectral assignments of methyl and ethyl xanthato complexes of nickel(II)

Assignments of the infrared frequencies of methyl and ethyl xanthato complexes of nickel(II) have been made with the aid of normal coordinate analyses. The assignments are discussed in relation to those in related molecules.

Infrared spectral assignments for transition metal thioxanthates

The i.r. frequencies of ethylthioxanthate complexes of some transition metals have been interpreted on the basis of normal coordinate treatments of the 1:1 molecular models. The band assignments are disscussed in comparison with those in closely related xanthate molecules.

Isotope shifts and hyperfine structure in the 555.8-nm S-1(0) -> P-3(1) line of Yb

We apply our technique of using a Rb-stabilized ring-cavity resonator to measure the frequencies of various spectral components in the 555.8-nm 1S0-->3P1 line of Yb. We determine the isotope shifts with 60 kHz precision, which is an order-of-magnitude improvement over the best previous measurement on this line. There are two overlapping transitions, 171Yb(1/2-->3/2) and 173Yb(5/2-->3/2), which we resolve by applying a magnetic field. We thus obtain the hyperfine constants in the 3P1 state of the odd isotopes with a significantly improved precision. Knowledge of isotope shifts and hyperfine structure should prove useful for high-precision calculations in Yb necessary to interpret ongoing experiments testing parity and time-reversal symmetry violation in the laws of physics.

Viscoelastic Properties of Nanocrystalline Films of Semiconducting Chalcogenides at Liquid/Liquid Interface

The interfacial shear rheological properties of a continuous single-crystalline film of CuS and a 3D particulate gel of CdS nanoparticles (3−5 nm in diameter) formed at toluene−water interfaces have been studied. The ultrathin films (50 nm in thickness) are formed in situ in the shear cell through a reaction at the toluene−water interface between a metal−organic compound in the organic layer and an appropriate reagent for sulfidation in the aqueous layer. Linear viscoelastic spectra of the nanofilms reveal solid-like rheological behavior with the storage modulus higher than the loss modulus over the range of angular frequencies probed. Large strain amplitude sweep measurements on the CdS nanofilms formed at different reactant concentrations suggest that they form a weakly flocculated gel. Under steady shear, the films exhibit a yield stress, followed by a steady shear thinning at high shear rates. The viscoelastic and flow behavior of these films that are in common with those of many 3D “soft” materials like gels, foams, and concentrated colloidal suspensions can be described by the “soft” glassy rheology model.

Molecular vibrations and conformation of primary dithiocarbamate ester. Infrared and NMR studies on S-methyl dithiocarbamate

The i.r. spectra of a primary dithiocarbamate ester namely, S-methyl dithiocarbamate (SMDTC) and its N-dideuterated compound have been measured between 4000 and 30 cm−1. Spectra in solution and at liquid nitrogen temperature have also been obtained. Assignment of all the fundamentals has been proposed and supported from a full normal coordinate analysis. The band assignments for SMDTC have been compared with those of related molecules and the characteristic bands of primary thioamides are derived. Conformational flexibility of SMDTC has been examined by i.r. and proton NMR spectroscopy. The hindered rotation around the C---N bond has been studied by a complete line shape analysis. The magnitude of ---NH2 and ---CH3 torsional barriers is also estimated from vibrational frequencies and force constants.

Temperature dependence of 35Cl NQR in 3,4-Dichlorophenol

NQR frequencies in 3,4-dichlorophenol are investigated in the temperature range 77 K to room temperature. Two resonances have been observed throughout the temperature range, corresponding to the two chemically inequivalent chlorine sites. Using Bayer's theory and Brown's method torsional frequencies and their temperature dependence in this range are estimated.

Nonlinear mode coupling of surface acoustic waves on an isotropic solid

The nonlinear mode coupling between two co-directional quasi-harmonic Rayleigh surface waves on an isotropic solid is analysed using the method of multiple scales. This procedure yields a system of six semi-linear hyperbolic partial differential equations with the same principal part governing the slow variations in the (complex) amplitudes of the two fundamental, the two second harmonic and the two combination frequency waves at the second stage of the perturbation expansion. A numerical solution of these equations for excitation by monochromatic signals at two arbitrary frequencies, indicates that there is a continuous transfer of energy back and forth among the fundamental, second harmonic and combination frequency waves due to mode coupling. The mode coupling tends to be more pronounced as the frequencies of the interacting waves approach each other.

A problem in micropolar elasticity

In this paper a three-dimensional analysis for statics and dynamics of a class of simply supported rectangular plates made up of micropolar elastic material is presented. The solution is in the form of series, in which each term is explicitly determined. For free vibrations, the frequencies are obtained by the solution of a closed form characteristic equation.

Temperature-dependence of 35Cl N.Q.R. in sodium chloroacetate

N.q.r. in sodium chloroacetate has been investigated at temperatures from 77 K to room temperature (c.300 K). A single line has been observed throughout this temperature range. Torsional frequencies of the molecule have been calculated in the above temperature range from Bayer's theory. Also the temperature coefficient of the torsional frequencies has been calculated by Brown's method.

Vibration of generally orthotropic skew plates

Vibration problem of generally orthotropic plates with particular attention to plates of skew geometry is studied. The formulation is based on orthotropic plate theory with arbitrary orientation of the principal axes of orthotropy. The boundary conditions considered are combinations of simply supported, clamped, and free-edge conditions. Approximate solution for frequencies and modes is obtained by the Ritz method using products of appropriate beam characteristic functions as admissible functions. The variation of frequencies and modes with orientation of the axes of orthotropy is examined for different skew angles and boundary conditions. Features such as "crossings" and "quasi-degeneracies" of the frequency curves are found to occur with variation of the orientation of the axes of orthotropy for a given geometry of the skew plate. It is also found that for each combination of skew angle and side ratio, a particular orientation of the axes gives the highest value for the fundamental frequency of the plate.

Vibration of skew plates

The vibration problems of skew plates with different edge conditions involving simple support and clamping have been considered by using the variational method of Ritz, a double series of beam characteristic functions being employed appropriate to the combination of the edge conditions. Natural frequencies and modes of vibration have been obtained for different combinations of side ratio and skew angle. These detailed studies reveal several interesting features concerning the frequency curves and nodal patterns. The results presented should, in addition, be of considerable value and practical significance in design applications.

Nonideal negative resistors and capacitors using an operational amplifier

Negative impedance converters (NIC's) may be used to realize negative driving-point impedances. The effect of the nonideal characteristics of the operational amplifier such as finite frequencydependent gain and output impedance on the performance of the negative impedances is analyzed. Detailed equivalent circuits showing the additional positive or negative inductive impedances due to the nonideal characteristics are given for negative resistance and negative capacitance realizations, and their relative performances are compared. The experimental results confirm the validity of the equivalent circuits. The effect of the slew rate of the operational amplifier on the maximum signal-handling capability (SHC) of the negative impedances at high frequencies is studied. Practical design considerations for achieving wider bandwidth as well as improved SHC are discussed.