Kinetics of phenyl radical reactions with propane,n‐butane,n‐hexane,and n‐octane: Reactivity of C6H5 toward the secondary C?H bond of alkanes

The kinetics of C₆H₅ reactions with n‐C_nH_2n+2 (n = 3, 4, 6, 8) have been studied by the pulsed laser photolysis/mass spectrometric method using C₆H₅COCH₃ as the phenyl precursor at temperatures between 494 and 1051 K. The rate constants were determined by kinetic modeling of the absolute yields of C₆H₆ at each temperature. Another major product C₆H₅CH₃ formed by the recombination of C₆H₅ and CH₃ could also be quantitatively modeled using the known rate constant for the reaction. A weighted least‐squares analysis of the four sets of data gave k (C₃H₈) = (1.96 ± 0.15) × 10¹¹ exp[?(1938 ± 56)/T], and k (n‐C₄H₁₀) = (2.65 ± 0.23) × 10¹¹ exp[?(1950 ± 55)/T] k (n‐C₆H₁₄) = (4.56 ± 0.21) × 10¹¹ exp[?(1735 ± 55)/T], and k (n?C₈H₁₈) = (4.31 ± 0.39) × 10¹¹ exp[?(1415 ± 65)T] cm³ mol^?1 s^?1 for the temperature range studied. For the butane and hexane reactions, we have also applied the CRDS technique to extend our temperature range down to 297 K; the results obtained by the decay of C₆H₅ with CRDS agree fully with those determined by absolute product yield measurements with PLP/MS. Weighted least‐squares analyses of these two sets of data gave rise to k (n?C₄H₁₀) = (2.70 ± 0.15) × 10¹¹ exp[?(1880 ± 127)/T] and k (n?C₆H₁₄) = (4.81 ± 0.30) × 10¹¹ exp[?(1780 ± 133)/T] cm³ mol^?1 s^?1 for the temperature range 297‐‐1046 K. From the absolute rate constants for the two larger molecular reactions (C₆H₅ + n‐C₆H₁₄ and n‐C₈H₁₈), we derived the rate constant for H‐abstraction from a secondary C? H bond, k_s?CH = (4.19 ± 0.24) × 10¹⁰ exp[?(1770 ± 48)/T] cm³ mol^?1 s^?1. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 36: 49–56, 2004     

Recent developments in algebraic combinatorics

We survey three recent developments in algebraic combinatorics. The first is the theory of cluster algebras and the Laurent phenomenon of Sergey Fomin and Andrei Zelevinsky. The second is the construction of toric Schur functions and their application to computing three-point Gromov-Witten invariants, by Alexander Postnikov. The third development is the construction of intersection cohomology for nonrational fans by Paul Bressler and Valery Lunts and its application by Kalle Karu to the torich-vector of a nonrational polytope. We also briefly discuss the “half hard Lefschetz theorem” of Ed Swartz and its application to matroid complexes. Partially supported by NSF grant #DMS-9988459.     

The Linear Rational Pseudospectral Method with Preassigned Poles

We present a linear rational pseudospectral (collocation) method with preassigned poles for solving boundary value problems. It consists in attaching poles to the trial polynomial so as to make it a rational interpolant. Its convergence is proved by transforming the problem into an associated boundary value problem. Numerical examples demonstrate that the rational pseudospectral method is often more efficient than the polynomial method.     

A new VOF‐based numerical scheme for the simulation of fluid flow with free surface. Part II: application to the cavity filling and sloshing problems

Finite element analysis of fluid flow with moving free surface has been performed in 2‐D and 3‐D. The new VOF‐based numerical algorithm that has been proposed by the present authors (Int. J. Numer. Meth. Fluids, submitted) was applied to several 2‐D and 3‐D free surface flow problems. The proposed free surface tracking scheme is based on two numerical tools; the orientation vector to represent the free surface orientation in each cell and the baby‐cell to determine the fluid volume flux at each cell boundary. The proposed numerical algorithm has been applied to 2‐D and 3‐D cavity filling and sloshing problems in order to demonstrate the versatility and effectiveness of the scheme. The proposed numerical algorithm resolved successfully the free surfaces interacting with each other. The simulated results demonstrated applicability of the proposed numerical algorithm to the practical problems of large free surface motion. It has been also demonstrated that the proposed free surface tracking scheme can be easily implemented in any irregular non‐uniform grid systems and can be extended to 3‐D free surface flow problems without additional efforts. Copyright © 2003 John Wiley & Sons, Ltd.     

Small Exotic Molecules with Bosonic Constituents

We study the stability and the properties of the ground state of neutral systems containing up to four positively charged bosons and their antiparticles. Examples are the di-pionium molecule (π ⁺ π ⁻)², which is almost identical to the positronium molecule (e ⁺ e ⁻)², the tri-pionium (π ⁺ π ⁻)³, and the quadri-pionium (π ⁺ π ⁻)⁴ molecules. We briefly compare our results on the energy to those on the large-N limit of (π ⁺ π ⁻) ^N . We also show that the annihilation probability can be calculated accurately with simple wave functions when one uses the generalized Schwinger rule. Received September 5, 1994; accepted for publication October 15, 1994     

Non-homogeneous equations of the thermoacoustics: Thermally forced radial thermo-elastic oscillations of the visco-thermal fluid sphere

The purpose of this paper is to solve the coupled non-homogeneous equations derived from the basic classical theory of the acoustic propagation in visco-thermal fluid. The 1D radial distribution of pressure and temperature inside a spherical object was found. It is supposed that both acoustic and thermal conditions on a surface of the object are known. The starting equations are considered in the time domain and their solution was found without initial conditions for steady harmonic motion.