The convergence properties of direct methods of energy minimization with respect to linear coefficients in the LCAO-MO-SCF approach

It is shown that in the LCAO-MO-SCF problem, if the molecular orbital orthonormality constraints are introduced in the manner first suggested by Fletcher, then the Hessian of the problem is singular. It is suggested that this singularity may well account for the slow convergence observed using direct energy minimization methods to solve the SCF problem. Ways of avoiding the consequences of this singularity are discussed.     

Molecular structure calculations without clamping the nuclei

A number of recent papers have considered ways in which molecular structure may be calculated when both the electrons and the nuclei are treated from the outset as quantum particles. This is in contrast to the conventional approach in which the nuclei initially have their positions fixed and so merely provide a potential for electronic motion. The usual approach is generally assumed to be justified by the 1927 work of Born and Oppenheimer. In this paper we discuss what precisely might be anticipated in the way of molecular structure from a mathematical consideration of the spectral properties of the full Coulomb Hamiltonian, to what extent the very idea of molecular structure might be dependent upon treating the nuclei simply as providing a potential and the extent to which the work of Born and Oppenheimer can be used to support this position.     

Non-empirical LCAO-MO-SCF-CI calculations on organic molecules with Gaussian type functions

This paper (Part I) describes the theoretical and computational bases of some non-empirical calculations on small organic molecules to be reported in later papers (Parts II et seq). Approximate solutions for the usual fixed nucleus electronic Hamiltonian, in the term of wave functions composed of Slater determinants, are discussed, with particular emphasis on their computational utility. Possible choices of basis functions, from which to form the determinants are examined, and the advantages of Gaussian type functions (GTF) centered on the component atoms are pointed out. Some of the properties of molecules which can be calculated using such approximate wave functions are outlined. Finally an attempt is made to discuss the current limitations of non-empirical calculations of the type described here, and some guesses are made about their future. Brief outlines as a set of appendices are given of the mathematical formalism and computational details of the calculations.     

A configuration interaction study of phosphine using bonded functions

A computational study is made of the effect of basis set upon the energy, properties and inversion barrier of the phosphine molecule. The calculations are performed at both the SCF and CI level. The flexibility of the double zeta basis is discussed in the light of the results.     

Uses and limitations of quantitative structure-activity relationships (QSARs) to categorize substances on the Canadian domestic substance list as persistent and/or bioaccumulative,and inherently toxic to non-human organisms

Under sections 73 and 74 of the revised Canadian Environmental Protection Act (CEPA 1999), Environment Canada and Health Canada must "categorize" and "screen" about 23,000 substances on the Domestic Substances List (DSL) for persistence (P), bioaccumulation (B), and inherently toxic (iT) properties. Since experimental data for P, B and iT are only available for a few DSL substances, a workshop was held to address issues associated with the use of Quantitative Structure-Activity Relationships (QSARs) to categorize these substances. This paper describes the results of an 11-12 November 1999 International Workshop sponsored by Environment Canada to discuss potential uses and limitations of QSARs to categorize DSL substances as either persistent or bioaccumulative and iT to non-human organisms and to recommend future research needed to develop methods for predicting the P, B and iT of difficult-to-model substances.     

Influence of microsupersonic gas jets on nanosecond laser percussion drilling

This paper reports on etching rates and hole quality for nanosecond laser percussion drilling of 200-μm thick 316L stainless steel performed with micro supersonic gas jets. The assist-gas jets were produced using nozzles of 200, 300 and 500 μm nominal throat diameters. Air and oxygen were used separately for the process gas in the drilling trials and the drilling performance was compared to drilling in ambient conditions. The highest etch rate of 1.2 μm per pulse was obtained in the ambient atmosphere condition, but this was reduced by about 50% with assist-air jets from the 200 μm nozzle. Increasing the jet diameter and/or using oxygen assist gas also decreased the etching rate and increased the hole diameter. The 200 μm nozzle using air-assist jets produced the least amount of recast and gave the best compromise for etching rate. A combination of plasma shielding and different gas dynamic conditions inside the holes and at the surface are correlated to the observations of different drilling rates and hole characteristics.     

Analysis of laser micro drilled holes through aluminium for micro-manufacturing applications

Conventional laser machining of aluminium with long wavelength lasers has its inherent problems due to the high reflectivity of aluminium to laser radiation (Handbook of Optics, vol 1, 2nd ed. New York: McGraw-Hill; 1995). Laser processing at shorter wavelengths reduces the reflectivity of the workpiece to the incident laser radiation and can also reduce the dimensions of the obtainable machining geometries. This paper reviews the limiting factors in the micro machining of aluminium using a diode pumped solid state (DPSS) Nd:YAG laser operated at 1064, 532, and 355 nm. The geometries of the laser-machined samples were investigated using interferometric, and optical methods to assess how the processing fluence and wavelength will affect the obtainable precision for successful integration of the laser in a micromachining CAD/CAM system.     

To what question is the clamped-nuclei electronic potential the answer?

An examination is made of how the nuclear motion Hamiltonian arises from a consideration of solutions to the eigenvalue problem for the full Coulomb Hamiltonian and the role played by the usual clamped-nuclei electronic Hamiltonian in the construction of such solutions.     

An analysis of the role of the Born--Oppenheimer approximation in calculating rotational--vibrational interactions in molecules

It is argued that whether the use of the Born--Oppenheimer approximation is thought to require consideration of the potential energy surface in the context of a full Coulomb Schr?dinger Hamiltonian in which translational and rotational motions are explicitly considered, and then it is inconsistent to treat that surface without allowing for the rotational motion of the molecule. Some of the implications of this upon the calculation of partition functions are considered.     

Probing active site geometry using high pressure and secondary isotope effects in an enzyme-catalysed 'deep' H-tunnelling reaction

We report the first study of the effects of hydrostatic pressure on α-2° KIEs for an enzyme-catalysed H-transfer reaction that occurs by 'deep' tunnelling. High pressure causes a significant decrease in the observed α-2° KIE on the pre-steady-state hydride transfer from NADH to FMN in the flavoprotein morphinone reductase. We have recently shown that high pressure causes a reduction in macroscopic reaction barrier width for this reaction. Using DFT vibrational analysis of a simple active site model, we posit that the decrease in α-2° KIE with pressure may arise due to a decrease in the vibrational coupling between the NADH primary (transferred) and secondary hydrogens in the 'tunnelling ready configuration', which more closely resembles the reactant state than the transition state.