Exact wave functions for few-particle systems: The choice of expansion for coulomb potentials

We discuss a procedure for calculating numerical Hartree–Fock orbitals that can be applied to polyatomic systems. This approach is formulated in momentum space to avoid Coulomb singularities and uses fast Fourier transforms to solve integral convolutions. Results for a number of simple systems are presented.     

Electron density distribution in potassium bis -(carbonato)cuprate(II)

The electron density distribution in potassiumbis-(carbonato)cuprate(II) has been analyzed using x-ray diffraction data from an earlier structure determination. While the copper-ligand geometry is close to square planar the deformation density near the metal is strongly asymmetric. There are local maxima near the copper atom along the line of the Cu-K vectors. These resemble features found in corresponding regions in normal length metal-metal bonds. The observation is consistent with the long range nature of the Coulomb potential associated with the potassium ion.     

Technique for incorporating the density functional Hessian into the geometry optimization of biomolecules, solvated molecules, and large floppy molecules

Traditional geometry optimization methods require the gradient of the potential surface, together with a Hessian which is often approximated. Approximation of the Hessian causes difficulties for large, floppy molecules, increasing the number of steps required to reach the minimum. In this article, the costly evaluation of the exact Hessian is avoided by expanding the density functional to second order in both the nuclear and electronic variables, and then searching for the minimum of the quadratic functional. The quadratic search involves the simultaneous determination of both the geometry step and the associated change in the electron density matrix. Trial calculations on Taxol indicate that the cost of the quadratic search is comparable to the cost of the density functional energy plus gradient. While this procedure circumvents the bottleneck coupled-perturbed step in the evaluation of the full Hessian, the second derivatives of the electron-repulsion integrals are still required for atomic-orbital-based calculations, and they are presently more expensive than the energy plus gradient. Hence, we anticipate that the quadratic optimizer will initially find application in fields in which existing optimizers breakdown or are inefficient, particularly biochemistry and solvation chemistry.     

Exactly Solvable su(N) Mixed Spin Ladders

It is shown that solvable mixed spin ladder models can be constructed from su(N) permutators. Heisenberg rung interactions appear as chemical potential terms in the Bethe Ansatz solution. Explicit examples given are a mixed spin- spin-1 ladder, a mixed spin- spin- ladder and a spin-1 ladder with biquadratic interactions.     

The eigenvalues of Kac's master equation

In this paper we derive formulae for the eigenvalues and spectral gap of the master equation for general collision kernels. We prove a conjecture of Mark Kac's on the existence of a spectral gap independent of the number of particles. We relate the eigenvalues to the “nonlinear” eigenvalues that occur in the exact solutions of model Boltzmann equations due to M. Ernst. Received: 30 November 2001; in final form: 26 March 2002/Published online: 2 December 2002     

Efficient computation of Fourier transforms on compact groups

This article genralizes the fast Fourier transform algorithm to the computation of Fourier transforms on compact Lie groups. The basic technique uses factorization of group elements and Gel'fand-Tsetlin bases to simplify the computations, and may be extended to treat the computation of Fourier transforms of finitely supported distributions on the group. Similar transforms may be defined on homogeneous spaces; in that case we show how special function properties of spherical functions lead to more efficient algorithms. These results may all be viewed as generalizations of the fast Fourier transform algorithms on the circle, and of recent results about Fourier transforms on finite groups. Acknowledgements and Notes. This paper was written while the author was supported by the Max-Planck-Institut für Mathematik, Bonn, Germany.     

Advances in methods and algorithms in a modern quantum chemistry program package

Advances in theory and algorithms for electronic structure calculations must be incorporated into program packages to enable them to become routinely used by the broader chemical community. This work reviews advances made over the past five years or so that constitute the major improvements contained in a new release of the Q-Chem quantum chemistry package, together with illustrative timings and applications. Specific developments discussed include fast methods for density functional theory calculations, linear scaling evaluation of energies, NMR chemical shifts and electric properties, fast auxiliary basis function methods for correlated energies and gradients, equation-of-motion coupled cluster methods for ground and excited states, geminal wavefunctions, embedding methods and techniques for exploring potential energy surfaces.     

The synthesis of azadirachtin: a potent insect antifeedant

We describe in full the first synthesis of the potent insect antifeedant azadirachtin through a highly convergent approach. An O-alkylation reaction is used to unite decalin ketone and propargylic mesylate fragments, after which a Claisen rearrangement constructs the central C8-C14 bond in a stereoselective fashion. The allene which results from this sequence then enables a second critical carbon-carbon bond forming event whereby the [3.2.1] bicyclic system, present in the natural product, is generated via a 5-exo-radical cyclisation process. Finally, using knowledge gained through our early studies into the reactivity of the natural product, a series of carefully designed steps completes the synthesis of this challenging molecule.     

GdAlO3 perovskite

Flux‐grown gadolinium aluminate perovskite, GdAlO₃, was examined using single‐crystal 0.7 Å‐wavelength synchrotron X‐ray diffraction. In the context of other well categorized rare earth aluminate (RAlO₃) perovskite phases, the orthorhombic Pnma symmetry determined for the current compound is unsurprising. Corner‐linked AlO₆ octahedra form the structural backbone of RAlO₃ perovskites and distort to accommodate the various rare earth ions in the structural voids. For GdAlO₃, the octahedral distortion, characterized by tilting of the octahedra about the shortest R—Al—R vectors, and octahedral deformation, characterized by strain of the octahedra along those axes, are in accordance with trends in the RAlO₃ series.