Intramolecular interactions of L‐phenylalanine: Valence ionization spectra and orbital momentum distributions of its fragment molecules

Intramolecular interactions between fragments of L ‐phenylalanine, i.e., phenyl and alaninyl, have been investigated using dual space analysis (DSA) quantum mechanically. Valence space photoelectron spectra (PES), orbital energy topology and correlation diagram, as well as orbital momentum distributions (MDs) of L ‐phenylalanine, benzene and L ‐alanine are studied using density functional theory methods. While fully resolved experimental PES of L ‐phenylalanine is not yet available, our simulated PES reproduces major features of the experimental measurement. For benzene, the simulated orbital MDs for 1e_1g and 1a_2u orbitals also agree well with those measured using electron momentum spectra. Our theoretical models are then applied to reveal intramolecular interactions of the species on an orbital base, using DSA. Valence orbitals of L ‐phenylalanine can be essentially deduced into contributions from its fragments such as phenyl and alaninyl as well as their interactions. The fragment orbitals inherit properties of their parent species in energy and shape (ie., MDs). Phenylalanine orbitals show strong bonding in the energy range of 14‐20 eV, rather than outside of this region. This study presents a competent orbital based fragments‐in‐molecules picture in the valence space, which supports the fragment molecular orbital picture and building block principle in valence space. The optimized structures of the molecules are represented using the recently developed interactive 3D‐PDF technique. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2011     

Kinetics of reaction of triethylammonium carboxylates with ethyl α‐halogenoacetate in various solvents

The kinetics of the reaction of ethyl α‐halogenoacetate with benzoic acid in the presence of triethylamine in aqueous acetone and in various solvents have been investigated. The rate constant of the reaction is 4–260 times higher in aprotic dipolar solvents than in protic solvents. The simple regression and multiple regression of log k₂ with various solvent parameters have led to the conclusion that in addition to the solvent polarity, various other solvent properties, together or individually, influence the reaction rate. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 894–900, 1999     

Unsteady flow past an impulsively started vertical plate with heat and mass transfer

Finite difference solution of the transient free-convection flow of an incompressible viscous fluid past an impulsively started semi-infinite vertical plate with heat and mass transfer is presented here. The steady state velocity, temperature and concentration profiles are shown graphically. Velocity profiles are compared with exact solution. It has been observed that there is a rise in the velocity due to the presence of a mass diffusion. An increase in Schmidt number, leads to a fall in the velocity. Stability and the convergence of the finite difference scheme are established. Received on 7 January 1998     

Kinetics and mechanism of the addition of iodine monochloride to some alkenes in nitrobenzene solvent. Effect of polarity of the solvent

The kinetics of the addition of iodine monochloride (ICl) to some vinyl compounds in nitrobenzene solvent was investigated. In all cases the reaction follows second order dependence on ICl and first order on the substrate, making the total order three. Rate constants were measured for each substrate at 20°, 30°, 40° and 50°C.Arrhenius plots were made from which activation energies were evaluated. Other kinetic and thermodynamic parameters are reported. A suitable mechanism is proposed for the reaction and based on this, the various parameters are discussed. Solvent effects are discussed and the data with nitrobenzene and acetic acid solvents are compared.

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Kinetik und Mechanismus der Addition vonICl zu einigen Alkenen in Nitrobenzol als Lösungsmittel. Effekt der Polarität des Lösungsmittels

Zusammenfassung Die Kinetik der Addition von ICl zu einigen Vinylverbindungen in Nitrobenzol als Lösungsmittel wurde untersucht. In allen Fällen ist die Reaktion von zweiter Ordnung hinsichtlich ICl und von erster Ordnung hinsichtlich des Substrats, d. h. mit einer Gesamtordnung von drei. Geschwindigkeitskonstanten wurden für jedes Substrat bei 20°, 30°, 40° und 50°C gemessen. AusArrhenius-Diagrammen wurden Aktivierungsenergien ermittelt und auch andere kinetische und thermodynamische Parameter wurden bestimmt. Ein Mechanismus wird vorgeschlagen, wobei die verschiedenen Parameter diskutiert werden. Lösungsmitteleffekte werden ebenfalls diskutiert und die Daten mit Nitrobenzol und Essigsäure als Lösungsmittel miteinander verglichen.

     

Orthogonal arrays: An introduction and their application in optimizing underrelaxation factors in ‘simple’-based algorithm

The primary aim of this paper is to demonstrate how the ‘design-of-experiments’ techniques which are successful in physical experiments could also be adapted to a numerical simulation code. As an example this technique is applied to a general finite difference code used for predicting three-dimensional turbulent recirculating flows. Here the equations for velocities and continuity are solved using the algorithm called SIMPLE, which stands for semi-implicit method for pressure-linked equations. Physical modelling of turbulence is taken care of by means of kinetic energy and turbulence dissipation rate equations. The objective is to optimize the underrelaxation factors of primary and secondary flow variables so that the number of iterations required for convergence is minimum. This is done by the orthogonal array technique (a particular type of design-of-experiment technique). The geometry considered for this purpose is that of a simple gas turbine can combustor and the study is restricted to the isothermal non-reacting condition. Tests are carried out on three different grid configurations. In each case the underrelaxation factor for velocities contributed most to speed up the rate of convergence. Also, for each grid configuration the underrelaxation factor settings for minimum iterations for convergence was found to be same. Hence it is proposed that when doing grid independence tests for any similar flow situation, all the underrelaxation factors could be optimized on coarse grids.