Effect of surface modes on the six-dimensional molecule-surface scattering dynamics of H2-Cu(100) and D2-Cu(111) systems

We include the phonon modes originating from the three layers of Cu(100)/Cu(111) surface atoms on the dynamics of molecular [H(2)(v,j)/D(2)(v,j)] degrees of freedom (DOFs) through a mean field approach, where the surface temperature is incorporated into the effective Hamiltonian (potential) either by considering Boltzmann probability (BP) or by including the Bose-Einstein probability (BEP) factor for the initial state distribution of the surface modes. The formulation of effective potential has been carried out by invoking the expression of transition probabilities for phonon modes known from the "stochastic" treatment of linearly forced harmonic oscillator (LFHO). We perform four-dimensional (4D?2D) as well as six-dimensional (6D) quantum dynamics on a parametrically time and temperature-dependent effective Hamiltonian to calculate elastic/inelastic scattering cross-section of the scattered molecule for the H(2)(v,j)-Cu(100) system, and dissociative chemisorption-physisorption for both H(2)(v,j)-Cu(100) and D(2)(v,j)-Cu(111) systems. Calculated sticking probabilities by either 4D?2D or 6D quantum dynamics on an effective potential constructed by using BP factor for the initial state distribution of the phonon modes could not show any surface temperature dependence. In the BEP case, (a) both 4D?2D and 6D quantum dynamics demonstrate that the phonon modes of the Cu(100) surface affect the state-to-state transition probabilities of the scattered H(2) molecule substantially, and (b) the sticking probabilities due to the collision of H(2) on Cu(100) and D(2) on Cu(111) surfaces show noticeable and substantial change, respectively, as function of surface temperature only when the quantum dynamics of all six molecular DOFs are treated in a fully correlated manner (6D).     

The effect of phonon modes on the H2(v, j)/D2(v, j)-Cu(1nn) scattering processes

We include the effect of the phonon modes originating from the three layers of Cu(1nn) surface atoms on the dynamics of incoming molecular [H(2)(v, j)/D(2)(v, j)] degrees of freedom (DOFs) through a mean-field approach, where the surface temperature is incorporated into the effective potential by considering Bose-Einstein probability (BEP) factor for the initial state distribution of the surface modes calculated within harmonic approximation. Such time and temperature dependent effective Hamiltonian is further subdivided assuming a weak coupling between the two sets of molecular DOFs, namely, (x, y, z, Z) and (X, Y), respectively, in particular, to reduce the computational cost and the corresponding coupled quantum dynamical equations of motion have been formulated in terms of Time Dependent Discrete Variable Representation (TDDVR) approach. We demonstrate the workability of TDDVR method to investigate the scattering of H(2)(v, j) on Cu(1nn) surface by calculating the reaction probabilities and scattering cross-sections. Calculated results show that the phonon modes affect (a) the state-to-state transition probabilities of the scattered H(2) molecule substantially but chemisorption and physisorption processes negligibly and (b) the reaction probability of the incoming D(2) molecule noticeably.     

Supramolecular Synthons in Designing Low Molecular Mass Gelling Agents: L‐Amino Acid Methyl Ester Cinnamate Salts and their Anti‐Solvent‐Induced Instant Gelation

Easy access to a class of chiral gelators has been achieved by exploiting primary ammonium monocarboxylate ( PAM ), a supramolecular synthon. A combinatorial library comprising of 16 salts, derived from 5 l ‐amino acid methyl esters and 4 cinnamic acid derivatives, has been prepared and scanned for gelation. Remarkably, 14 out of 16 salts prepared (87.5 % of the salts) show moderate to good gelation abilities with various solvents, including commercial fuels, such as petrol. Anti‐solvent induced instant gelation at room temperature has been achieved in all the gelator salts, indicating that the gelation process is indeed an aborted crystallization phenomenon. Rheology, optical and scanning electron microscopy, small angle neutron scattering, and X‐ray powder diffraction have been used to characterize the gels. A structure‐property correlation has been attempted, based on these data, in addition to the single‐crystal structures of 5 gelator salts. Analysis of the FT‐IR and ¹H NMR spectroscopy data reveals that some of these salts can be used as supramolecular containers for the slow release of certain pest sex pheromones. The present study clearly demonstrates the merit of crystal engineering and the supramolecular synthon approach in designing new materials with multiple properties.     

Boundary element method for wave trapping by a multi-layered trapezoidal breakwater near a sloping rigid wall

This study examines the multiple layers in a rubble mound breakwater and their effect on reflection and dissipation of incoming ocean waves. The numerical model is developed using multi-domain boundary element method for oblique water wave trapping near a sloping wall by a multi-layered trapezoidal porous structure, which is utilized to model armour, filter and core layers while examining the hydrodynamics in different configurations. Both, the constant element and linear element approaches to boundary element method are discussed. The cases of bottom-standing porous structures as being submerged and fully extended are considered. The wave hydrodynamics over the structure is described by the reflection and dissipation coefficients along with the forces acting on the sloping wall, and is influenced by wave and structural parametrics of the system. The influence of armour layer in different configurations is highlighted for various structural and wave parameters.

     

Effect of Second Order Chemical Reaction on MHD Free Convective Radiating Flow over an Impulsively Started Vertical Plate

An attempt has been made to study laminar convective heat and mass transfer flow of an incompressible, viscous and electrically conducting fluid over an impulsively started vertical plate with conduction-radiation embedded in a porous medium in presence of transverse magnetic field. The influence of both second order chemical reaction and heat generation are taken into account. The governing coupled partial differential equations are solved by Crank-Nicolson method. The effects of important physical parameters on the velocity, temperature and concentration have been analyzed through graphs. The results of the present study agree well with the previous solutions. Applications of the present study are shown in material processing systems and different industries. The important findings of present study are: chemical reaction parameter acts as resistive force to reduce the velocity whereas heat source parameter enhances the velocity.     

Theoretical study of excited state proton transfer in pyrrole-2-carboxylic acid

Pyrrole 2-carboxylic acid (PCA) shows dual emission (310 nm and 430 nm) in water on photo-excitation, which indicates that more than one species is in the excited state. This paper reports on the quantum chemical analysis of pyrrole 2-carboxylic acid (PCA) in the light of a possible excited state proton transfer. Dipole moment, excited state energy and findings in molecular orbital calculations (HOMO, LUMO) establish that PCA is a likely candidate for transfer of a proton from the pyrrole moiety to the C=O of carboxylic moiety (possible zwitterionic form) in the excited state. Overall, the computed predicted results of intramolecular and intermolecular excited state proton transfer corroborates the experimental results.     

GC-MS and GC-FTIR identification of volatile radiolytic products in water-nitrobenzene-carbon tetrachloride two phase systems

Various volatile products formed in the -radiolysis of water-nitrobenzene-carbon tetrachloride two phase systems have been identified using GC-MS and GC-FTIR systems. The conditions for the separation of the products are described in detail. It was found that product formation is dependent on the composition of the systems. In case when the volume ratio of carbon tetrachloride is higher, chlorobenzene appears to be one of the major radiolytic products. This means that substitution of the nitro group by chlorine atom occurs in the presence of water. Substitution of the nitro group and hydrogen atom by chlorine atom and/or HO free radical is also observed, depending on the composition of the mixture. Formation of phenyl isocyanate is proposed to be the result of interaction of dichlorocarbene and nitrobenzene. The mechanism of some main product formation is described briefly.This paper constitutes part of the Ph.D. thesis of M. K. SAHOO and was presented at the 9th Czecho-Slovak Spectroscopic Conference with International Participation, eské Budjovice, C.S.F.R., June 22–24, 1992.     

Infrared and Raman spectroscopies of InP/II–VI core-shell nanoparticles

We use infrared (IR) and Raman spectroscopies to investigate the optically active phonon modes in InP nanoparticles and InP/II–VI core-shell nanoparticles fabricated by similar colloidal chemistry methods. The IR transmission spectra of several InP nanoparticle samples exhibit a common absorption feature, which we assign to the Fröhlich mode. The Raman results for the same samples show transverse and longitudinal optical phonon peaks, and scattering strength in between due to surface optical (SO) modes. Infrared spectra of the InP/ZnSe core-shell nanoparticles () exhibit three absorption features, one due to the InP core, and the others associated with the ZnSe shell layer. Raman measurements (12–292 K) also show three phonon-related peaks, whose intensities vary sharply with temperature. The frequencies of the IR and Raman lines are in approximate accord with dielectric continuum theory.