Categorical Aspects in Projective Geometry

After introducing morphisms between projective geometries, some categorical questions are examined. It is shown that there are three kinds of embeddings and two kinds of quotients. Furthermore the morphisms decompose in a canonical way into four factors.     

New Expressions for Depolarization Dyadics in an Axially Uniaxial Bianisotropic Medium

Novel expressions for the depolarization dyadics in an axially uniaxial bianisotropic medium (AUBM) are presented. Explicit formulae for the depolarization dyadics are derived for cubical, cylindrical and spherical geometries and their dependence on the magnetoelectric coupling parameter is studied graphically.     

Improved linear interpolation practice for finite‐volume schemes on complex grids

Methods for the computation of flow problems based on finite‐volume discretizations and pressure‐correction methods frequently require the interpolation of control volume face values from nodal values. The simple, often employed central differencing scheme (CDS) leads to a significant loss in accuracy when the numerical grid is non‐regular as it is usual when modelling complex geometries. An alternative technique based on a multi‐dimensional Taylor series expansion (TSE) is proposed, which preserves the CDS‐like sparsity pattern of the discrete system. While the TSE scheme computationally is only slightly more expensive than the CDS approach, it results in a significantly higher accuracy, where the difference increases with the grid irregularity. The method is investigated and compared to the CDS approach for some representative test cases. Copyright © 2002 John Wiley & Sons, Ltd.     

INDO Calculations with inclusion of an effective solvent field. Application to benzosemiquinones

Theoretical Chemistry Accounts - An INDO method extended to include a contribution from the solvent by means of an effective solvent field (ESF) is applied to the three isomeric benzosemiquinones...     

Semiempirical valence-electron calculations of excited state geometries and vibrational frequencies

Summary The use of finite differences and finite second differences in order to approximate gradients and second derivatives of the energy for geometry optimization and determination of normal modes of vibration on the CI level of computation is discussed in connection with the semiempirical MNDOC-CI valence electron method. Results are given for ground and excited states of ethylene, acetylene, formaldehyde, acetaldehyde, acetone, formamide and acetamide and are compared with experimental andab initio data. Mean absolute errors for bond lengths, bond angles, excitation energies and vibrational frequencies indicate that the MNDOC-CI method is well suited to describe ground and excited states of organic molecules on the same level of approximation and with comparable accuracy.     

Excited states of acetylene: a CASPT2 study

Valence and low-lying Rydberg states of acetylene (C₂H₂) are reexamined in the singlet as well as in the triplet manifold. The major goal of this work is a better understanding of the valence states that contribute to the low-energy electron-energy-loss spectrum recorded under conditions where transitions to triplet states are enhanced. An appropriate theoretical treatment of these states has to include the low-lying Rydberg states because of their energetic proximity to some of the valence states. The CASSCF/CASPT2 method provides a suitable framework for such a task. For some important states the geometry was optimized at the CASPT2 level to allow a comparison with the results of other highly accurate methods that have been applied to acetylene in the past. Received: 11 June 1998 /Accepted: 30 July 1998 / Published online: 19 October 1998     

Basis set effects on calculated geometries: 6-311++G** vs. aug-cc-pVDZ

The effect of basis sets on MP2 and CCSD calculated geometries has been investigated for a series of small organic molecules with two to four nonhydrogen atoms. Whereas 6-311++G** usually leads to satisfactory structures, this was not true with aug-cc-pVDZ, although it uses more basis functions than the former set. In addition, the smaller 6-311++G** invariably leads to lower calculated energies than aug-cc-pVDZ. With a given basis set, CCSD gives more satisfactory calculated geometries than MP2, but with a much greater computation time. For the compounds in this report, B3LYP/6-311++G** is quite effective in giving satisfactory calculated geometries at a relatively small computational cost.     

Momentum density and molecular geometry. Bent BH 2 − and linear BH 2 +

Based on a special form of the molecular virial theorem, the recently proposed method of momentum density for interatomic interactions is here applied to the problem of molecular geometry. Two molecules BH ₂ ^– and BH ₂ ⁺ , which have the same nuclear framework but favor respectively bent and linear conformations, are comparatively studied. Using an approximate Hartree-Fock momentum density, the total molecular energy (including the nuclear repulsion) is partitioned into orbital components, and a geometry correlation diagram is derived. An atom-bond partitioning of the total energy is also examined based on the one- and two-center decomposition of the momentum density.     

SU(3)-manifolds of cohomogeneity one

In this article, we classify 7- and 8-dimensional manifolds M admitting an SU(3) action of cohomogeneity one such that (i) M is simply connected and the orbit space M/G is isomorphic to [0, 1], and (ii) \({M/G\cong S^{1}}\) and the principal orbits are simply connected. We discuss applications to the study of the group manifold SU(3) and to 8-dimensional quaternion-Kähler spaces, and links between dimension 7 and 8 given by circle actions.