Angular distributions of photoelectrons emitted from fixed-in-space
molecules have become an exciting new tool for studying electronic
structure and dynamics. We here use multiple scattering
photoelectron diffraction (MSPD) theory to calculate
the final-state wavefunction of the electron leaving the molecule and then
subsequently its angular distribution. The effects of non-spherical
scattering potentials are included in our formalism through non-diagonal
scattering matrices, which fit directly into a new approach for multiple
scattering theory originally based on spherical potentials.
When the kinetic energy of the photoelectron is low (E < 50-100 eV),
we find that its scattering cannot be adequately represented by
spherically-symmetric potentials. In addition, we have considered
the effect of the final-state hole on the wavefunction, and found
this to be important as well. Different polarizations of the
light are also included. As an example, we calculate the
angular distribution of photoelectrons emitted from the K shells of C
and O in oriented gas-phase CO molecules, as recently measured by
several groups. We show that intramolecular scattering and
interference are responsible for the experimentally measured patterns.
Particularly important are the energies for which shape resonances appear
in the continuum, with the angular distributions showing radical changes
over such resonances. We find good agreement between our theoretical
results and recent experimental measurements. This MSPD
approach thus represents a more accurate and versatile method for dealing
with such angular distributions as compared to prior
calculations of such effects.
Last updated July 2003
Ricardo Díez Muiño rdm@sc.ehu.es