The use of tetraalkylphosphonium–tetrafluoroborate–tetrafluoroboric acid in the curing of a liquid crystalline epoxy resin

Tetraalkylphosphonium–Tetrafluoroborate–Tetrafluoroboric Acid was used as a catalyst in the curing of a liquid crystalline epoxy. Under some conditions the Tetraalkylphosphonium–Tetrafluoroborate–Tetrafluoroboric Acid actually retarded the reaction. An extensive experimental and kinetic analysis is presented anda mechanism for the reaction retardation is proposed. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1457–1471, 1998     

Reactions of phosphoric anhydride with acyclic amides. Synthesis of amidines and imides

Acyclic secondary amides such as benzanilides 1a–g , acetanilides 2a–d , and benzamide 1h undergo self-condensation in the presence of phosphoric anhydride to produce, in one step, N-substituted aroyl benzamidines 3a–g , acyl acetamidines 4a–d , and imide 5 , respectively. Mechanistic evidence is presented for nucleophilic attack by the iminol tautomers on the O-phosphorylated amides to give amidines and on the N-phosphorylated imidates to give imides. © 1998 John Wiley & Sons, Inc. Heteroatom Chem 9:261–263, 1998     

Oxygen diffusion in poly(methyl methacrylate) at low temperatures

Oxygen diffusion in atactic poly(methyl methacrylate) has been studied by anthracene luminescence quenching in geminate pairs anthracene-oxygen at 77–130 K. Analysis of the experimental data shows that the luminescence quenching is well accounted for by a polychromatic model assuming a log-normal diffusion coefficients distribution due to inhomogeneity of polymer structure. Energy activation is equal to 30 ± 1 KJ/mol. All diffusion coefficients data in the range 77–300 K demonstrate a good linear Arrhenius law. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36 : 127–131, 1998     

How good is a Broyden–Fletcher–Goldfarb–Shanno-like update Hessian formula to locate transition structures? Specific reformulation of Broyden–Fletcher–Goldfarb–Shanno for optimizing saddle points

Based on a study of the Broyden–Fletcher–Goldfarb–Shanno (BFGS) update Hessian formula to locate minima on a hypersurface potential energy, we present an updated Hessian formula to locate and optimize saddle points of any order that in some sense preserves the initial structure of the BFGS update formula. The performance and efficiency of this new formula is compared with the previous updated Hessian formulae such as the Powell and MSP ones. We conclude that the proposed update is quite competitive but no more efficient than the normal updates normally used in any optimization of saddle points. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 349–362, 1998     

Kramers' unrestricted Hartree–Fock and second-order Møller–Plesset perturbation methods using relativistic effective core potentials with spin–orbit operators: Test calculations for HI and CH3I

The Kramers' restricted Hartree–Fock (KRHF) and second-order Møller–Plesset perturbation (KRMP2) methods using relativistic effective core potentials (RECP) with spin–orbit operators and two-component spinors are extended to the unrestricted forms, KUHF and KUMP2. As in the conventional unrestricted methods, the KUHF and KUMP2 methods are capable of qualitatively describing the bond breaking for a single bond. As a result, it is possible to estimate spin–orbit effects along the dissociation curve at the HF and MP2 levels of theory as is demonstrated by the test calculations on the ground states of HI and CH₃I. Since the energy lowering due to spin–orbit interactions is larger for the I atom than for the closed-shell molecules, dissociation energies are reduced and bond lengths are slightly elongated by the inclusion of the spin–orbit interactions. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 66 : 91–98, 1998     

Use of symmetric rank-one Hessian update in molecular geometry optimization

The use of the symmetric rank-one Hessian update and the Broyden–Fletcher–Goldfarb–Shano (BFGS) update formula are considered in an ab initio molecular geometry optimization algorithm. It is noted that the symmetric rank-one Hessian update has an advantage when compared with the BFGS update formula and this advantage must be more evident in the optimization of molecular geometry, because the total energy surface is a near-quadratic function with a small nonlinearity close to a minimum point. The results obtained in geometry optimization of a test group of molecules support this proposal and show that the use of the symmetric rank-one Hessian update formula permits reduction of the number of energy and gradient evaluations needed to locate a minimum on the energy surface. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 1877–1886, 1998     

Parallel pseudospectral electronic structure: II. Localized Møller–Plesset calculations

We have developed a parallel version of our pseudospectral localized Møller–Plesset electronic structure code. We present timings for molecules up to 1010 basis functions and parallel speedup for molecules in the range of 260–658 basis functions. We demonstrate that the code is scalable; that is, a larger number of nodes can be efficiently utilized as the size of the molecule increases. By taking advantage of the available distributed memory and disk space of a scalable parallel computer, the parallel code can calculate LMP2 energies of molecules too large to be done on workstations. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 1030–1038, 1998     

Equation of state of poly(dimethylsiloxane) melts

The pressure–volume–temperature (PVT) properties of three commercial samples of poly(dimethylsiloxane) are studied experimentally and theoretically in the temperature range 25–150°C and for pressure to ∼ 3 kbar. The Tait equation is employed to represent the data at elevated pressure. Isothermal compressibilities are computed for the three samples. The melt data are analyzed in terms of the Simha–Somcynsky hole theory, and scaling parameters of pressure, volume, and temperature are obtained. Satisfactory agreement between theory and experiment is found over the entire range of experimental pressures. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 841–850, 1998     

Spin–orbit and correlation effects in platinum hydride (PtH)

The low-lying electronic states of PtH were studied by all-electron one- and two-component variational calculations on the multireference CI levels. The orbital optimization is performed within a one-component formalism, whereas the further refinement of the wave functions follows two different schemes: The most demanding approach introduces spin–orbit coupling in the CI optimization step, giving a simultaneous treatment of electron correlation and spin–orbit coupling. The second, considerably less demanding approach, corresponds almost to a perturbational treatment, introducing spin–orbit coupling as a final step after the CI optimization by diagonalizing the resulting Hamiltonian matrix over CI states. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 68: 53–64, 1998     

Extension of the quantum virial and Hellmann–Feynman theorems to the quantum statistical averages

In the present article, we extended the quantum virial and Hellmann–Feynman theorems to the quantum statistical averages, that is, to the thermal states. We obtained some new formulas which make possible expressing the thermodynamical observables of the system as functions of the moments of coordinates, as we see in a short example relating to the pseudoharmonical oscillator. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 69: 159–165, 1998     

The acetolysis of 2-acetoxyalkyltellurium trihalides

The reaction of six 2-acetoxyalkyltellurium trihalides in refluxing dry acetic acid yields haloacetates in addition to the previously observed diacetates. The haloacetates are formed either through direct cleavage of the carbon–tellurium bond with retention of configuration or through initial formation of a neighboring group intermediate that is subsequently attacked by halide ion. Added lithium acetate leads to an increase in S_N2 attack on the tellurium carbon. © 1998 John Wiley & Sons, Inc. Heteroatom Chem 9:85–93, 1998     

Multi-multigrid solution of modified Poisson–Boltzmann equation for arbitrarily shaped molecules

A new multi-multigrid method is presented for solving the modified Poisson–Boltzmann equation based on the Kirkwood Hierarchy of equations, with Loeb's closure, on a three-dimensional grid. The results are compared with standard Poisson–Boltzmann calculations, which are known to underestimate the local concentration of counterions near charged parts of molecules, mainly due to neglect of fluctuations in the ionic concentrations. In the present study, the Kirkwood hierarchy of equations is discretized with the finite volume method and solved using multigrid techniques. The new possibility for solution of the three-dimensional modified Poisson–Boltzmann equation, for the first time within a model including a dielectric discontinuity, and within reasonable computational time, enables the calculation of higher valence ion distributions around arbitrarily shaped biological macromolecules. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 893–901, 1998     

Synthesis and reactions of a poly(methacrylate) from an optically active amino alcohol

Synthesis and radical polymerization of a novel optically active methacrylate, (S)–2–tert–butoxycarbonylamino–3–phenylpropyl methacrylate (MA–F–BOC), were examined. MA–F–BOC was synthesized from methacrylic acid and N–protected (L)–phenylalaninol. Radical polymerization of MA–F–BOC quantitatively afforded the corresponding polymethacrylate with a relatively high molecular weight. Radical copolymerizations of MA–F–BOC were carried out with styrene and acrylamide to afford the copolymers. Radical polymerization of MA–F–BOC in the presence of n–butanethiol afforded the oligomers, whose degrees of polymerizations were 3.3–8.0. The BOC group was completely cloven with HBr to afford the corresponding optically active polymeric amine quantitatively. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 1981–1986, 1998     

Dyson-corrected orbital energies for the perturbative treatment of electron correlation

The effect of replacing the Hartree–Fock one-particle energies with ionization potentials obtained from inverse Dyson equation when calculating electron correlation energies perturbatively is investigated. Though the energy shifts vary from system to system, the slight decrease of the resulting excitation energies at around equilibrium geometries leads to a slight increase of the correlation energies in most cases. In the dissociation limit the inverse Dyson equation opens the gap, thus nondiverging potential curves emerge even at the restricted Hartree–Fock (RHF)+RS2 level. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 69: 713–719, 1998     

Calculation of clustered eigenvalues of large matrices using variance minimization method

The autoadjusting perturbation theory method is presented and developed to calculate eigenpairs of a square matrix. The procedures to simultaneously compute a cluster of eigenpairs by variance minimization are also given. Finally, numerical examples are reported. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 1777–1785, 1998     

Relation between BCS Hamiltonian and Ginzburg–Landau equation

It is intended to derive the Ginzburg–Landau (GL) equation directly from the Bardeen–Cooper–Schrieffer (BCS) Hamiltonian. By the use of the Hubbard–Stratonovitch transformation, the electron–electron interaction composed of four fermion operators is eliminated to yield an auxiliary boson field. This is an effective field in which electrons behave as if they were free. In applying the path integral method, the electron field is integrated out to remain the Lagrangian for this boson field. The symmetry breaking and the phase transition of the system described by this field are discussed, and it is shown that this boson field turns out to be the GL order parameter. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 69: 693–703, 1998     

Effect of available volumes on radial distribution functions

The traditional method of analyzing solution structuring properties of solutes using atom–atom radial distribution functions (rdfs) can give rise to misleading interpretations when the volume occupied by the solute is ignored. It is shown by using the examples of O(4) in α- and β-D-allose that a more reliable interpretation of rdfs can be obtained by normalising the rdf using the available volume, rather than the traditional volume of a spherical shell. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 363–367, 1998     

Polymerization by oxidative coupling: Discovery and commercialization of PPO® and Noryl® resins

The discovery of oxidative polymerization and the commercial development of PPO® and Noryl® resins is described. The scope of the oxidative polymerization reaction is discussed. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 505–517, 1998     

A parallel Green's operator for multidimensional quantum scattering calculations

A parallel algorithm for computing multidimensional scattering wave functions is introduced. The inhomogeneous scattering (Lippmann–Schwinger) equation is solved within the discrete variable representation with absorbing boundary conditions, using iterative (Krylov) methods. A parallel Green's operator enables one to distribute the wave function to orthogonal subspaces in which it is processed in parallel. Application to a model problem of electron scattering in a three-dimensional rectangular quantum wire is given. Speedup is demonstrated with an increasing number of processors and with increasing dimensions and/or sampling density. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 69: 167–173, 1998