Reaction of t-butoxy radicals with norbornadiene

95 percent of the reaction of t-butoxy radical with norbornadiene occurs by radical addition followed by rearrangement to nortricyclyl and 7-t-butoxynorbornenyl products; the remainder includes a novel radical rearrangement involving a 1,3-H shift and some radical abstraction observed for the first time.     

Total lattice potential energy of sodium bromide dihydrate NaBr · 2H2O

In addition to presenting comparative calculations by two approaches for the total lattice potential energy of sodium bromide dihydrate, NaBr · 2H₂O, found to take the value 803.9 kJ mol^-1, we investigate the influence of the size and nature of the basis set used to generate multipole moments in a Hartee-Fock calculation which are in turn used to calculate the Madelung constant. The requirement is one of critical size of the basis set and once this is reached the electrostatic energy will be reliable.     

Photothermal degradation of copolymers of methyl methacrylate and n-butyl acrylate

The photothermal degradation of copolymers of methyl methacrylate (MMA) and n-butyl acrylate (n-BuA) covering the whole composition range has been studied at 165°.The gaseous products, which are relatively minor, are hydrogen, carbon monoxide and methane. The liquid products are predominantly MMA, with n-BuA, n-butanol and n-butyraldehyde as minor products. Infra-red spectral changes in the residue were attributed to lactone formation and associated with butanol formation as in the purely thermal reaction The “cold ring” or chain fragment fraction becomes increasingly more abundant as the n-BuA content of the copolymer is increased.All the products and principal features of the reaction are explained in terms of a radical process which is initiated by scission of pendant acrylate units and is propagated by a combination of depropagation and intra- and intermolecular transfer processes, the relative importance of which depends upon copolymer composition. Differences from the thermal reaction and the corresponding reaction in copolymers of methyl methacrylate and methyl acrylate are discussed.     

A three-stage variable-shift iteration for polynomial zeros and its relation to generalized rayleigh iteration

Summary We introduce a new three-stage process for calculating the zeros of a polynomial with complex coefficients. The algorithm is similar in spirit to the two stage algorithms studied by Traub in a series of papers. We prove that the mathematical algorithm always converges and show that the rate of convergence of the third stage is faster than second order. To obtain additional insight we recast the problem and algorithm into matrix form. The third stage is inverse iteration with the companion matrix, followed by generalized Rayleigh iteration.This work was supported in part by the National Science Foundation and the Office of Naval Research.     

Thermochemistry of azide salts and the azide ion using direct minimisation equations to obtain the lattice energy of the univalent azide salts

The opportunity to test a new equation for the computation of the lattice energy and at the same time examine a disparity in the literature data for the enthalpy of formation of the azide ion, $\text{ΔH}{}^{\mathrm{\theta }}{}_{\mathrm{?}}\text{(}\text{N}{}_3{}^{\mathrm{?}}\text{) (}\text{g}\text{)}$ was the motivation for this study. The results confirm our earlier calculation and show the new equation to be reliable. Thermodynamic data produced in the study take values: $\text{ΔH}{}^{\mathrm{\theta }}{}_{\mathrm{?}}\text{(}\text{N}{}_3{}^{\mathrm{?}}\text{)(}\text{g}\text{) = 144}\text{kJ mor}{}^{\mathrm{?1}}$ΔH^θ_hyd(N₃^?) = ?315 KJ mol^?1 or ΔH^θ_hyd(N₃^?) = ?295 KJ mol^?1U_POT(NaN₃) = 732 kJ mol^?1U_POT(KN₃) = 659 kJ mol^?1U_POT(RbN₃) = 637 kJ mol^?1U_POT(CsN₃) = 612 kJ mol^?1U_POT(TIN₃) = 689 kJ mol^?1. The lattice energies of azides whose enthalpies of formation are documented have been calculated as well as the enthalpy of formation of the azide radical.