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A hybridGaussian-discrete variable representation approach to molecular continuum processes II: application to photoionization of diatomic Li2+

Journal Article · · Physical Review A
OSTI ID:936615
We describe an approach for studying molecular photoionization with a hybrid basis that combines the functionality of analytic basis sets to represent electronic coordinates near the nuclei of a molecule with numerically-defined grid-based functions. We discuss the evaluation of the various classes of two-electron integrals that occur in a hybrid basis consisting of Gaussian type orbitals (GTOs) and discrete variable representation (DVR) functions. This combined basis is applied to calculate single photoionization cross sections for molecular Li_2+, which has a large equilibrium bond distance (R=5.86a_0). The highly non-spherical nature of Li_2+ molecules causes higher angular momentum components to contribute significantly to the cross section even at low photoelectron energies, resulting in angular distributions that appear to be f-wave dominated near the photoionization threshold. At higher energies, where the de Broglie wavelength of the photoelectron becomes comparable with the bond distance, interference effects appear in the photoionization cross section. These interference phenomena appear at much lower energies than would be expected for diatomic targets with shorter internuclear separations.
Research Organization:
Ernest Orlando Lawrence Berkeley National Laboratory, Berkeley, CA (US)
Sponsoring Organization:
Chemical Sciences Division
DOE Contract Number:
AC02-05CH11231
OSTI ID:
936615
Report Number(s):
LBNL-868E
Journal Information:
Physical Review A, Journal Name: Physical Review A; ISSN 1050-2947; ISSN PLRAAN
Country of Publication:
United States
Language:
English