The continuum molecular orbitals arising from L-2 calculations using special polynomial Gaussian functions are accurately tested to probe their capability in producing accurate photoemission cross sections. The molecular potential is represented by the local X alpha approximation, which permits a comparison with numerically integrated (exact) orbitals. Several strong anisotropic molecules are taken into account to check the flexibility of the L-2 bases in the presence of strong attractive potentials. This work shows that for adequate choices of Gaussian functions, phase shifts may be estimated with reasonable accuracy while the errors in the continuum transition probabilities are within 2-3% in the more unfavourable cases. Therefore, the proposed basis sets appear to be suitable for the description of the electronic continuum in molecular photoionization calculations.
Performance of polynomial Gaussian functions in describing the molecular electronic continuum
CACELLI, IVO
1997-01-01
Abstract
The continuum molecular orbitals arising from L-2 calculations using special polynomial Gaussian functions are accurately tested to probe their capability in producing accurate photoemission cross sections. The molecular potential is represented by the local X alpha approximation, which permits a comparison with numerically integrated (exact) orbitals. Several strong anisotropic molecules are taken into account to check the flexibility of the L-2 bases in the presence of strong attractive potentials. This work shows that for adequate choices of Gaussian functions, phase shifts may be estimated with reasonable accuracy while the errors in the continuum transition probabilities are within 2-3% in the more unfavourable cases. Therefore, the proposed basis sets appear to be suitable for the description of the electronic continuum in molecular photoionization calculations.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
