Approximate ab initio calculations and the method of molecular fragments

A two stage approach to performing ab initio calculations on medium and large sized molecules is described. The first step is to perform SCF calculations on small molecules or molecular fragments using the OPIT Program. This employs a small basis set of spherical and p-type Gaussian functions. The Gaussian functions can be identified very closely with atomic cores, bond pairs, lone pairs, etc. The position and exponent of any of the Gaussian functions can be varied by OPIT to produce a small but fully optimised basis set. The second stage is the molecular fragments method. As an example of this, Gaussian exponents and distances are taken from an OPIT calculation on ethylene and used unchanged in a single SCF calculation on benzene. Approximate ab initio calculations of this type give much useful information and are often preferable to semi-empirical approaches, since the nature of the approximations involved is much better defined.

3-body energy terms in a quartet state of H3

Calculations of the 3-body energy term in a quartet (4A2 ) state of H3 (equilateral triangle nuclear-configurations) show a minimum in the 3-body energy for a side length of about 1.3 bohrs.

Discrete breathers in a two-dimensional Fermi-Pasta-Ulam lattice

Using asymptotic methods, we investigate whether discrete breathers are supported by a two-dimensional Fermi-Pasta-Ulam lattice. A scalar (one-component) two-dimensional Fermi-Pasta-Ulam lattice is shown to model the charge stored within an electrical transmission lattice. A third-order multiple-scale analysis in the semi-discrete limit fails, since at this order, the lattice equations reduce to the (2+1)-dimensional cubic nonlinear Schrödinger (NLS) equation which does not support stable soliton solutions for the breather envelope. We therefore extend the analysis to higher order and find a generalised $(2+1)$-dimensional NLS equation which incorporates higher order dispersive and nonlinear terms as perturbations. We find an ellipticity criterion for the wave numbers of the carrier wave. Numerical simulations suggest that both stationary and moving breathers are supported by the system. Calculations of the energy show the expected threshold behaviour whereby the energy of breathers does {\em not} go to zero with the amplitude; we find that the energy threshold is maximised by stationary breathers, and becomes arbitrarily small as the boundary of the domain of ellipticity is approached.