Floating s- and p-type Gaussian Orbitals

The advantages of including a small number of p-type gaussian functions in a floating spherical gaussian orbital calculation are pointed out and illustrated by calculations on molecules which previously have proved to be troublesome. These include molecules such as F2 with multiple lone pairs and C2H2 with multiple bonds. A feature of the results is the excellent correlation between the orbital energies and those of a double zeta calculation reported by Snyder and Basch.

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.