Pade-approximant corrections to general variational expressions of scattering theory: Application to 5sigma photoionization of carbon monoxide
We discuss a method for systematically correcting results obtained using variational expressions in scattering theory. The approach taken is to compute a sequence of Pade approximants of the form (N/N) for the error in an initial variational estimate obtained using a basis-set expansion. The relationship between the Pade-approximant approach and the iterative Schwinger method for correcting variational estimates is also examined. We discuss a large class of general variational expressions to which the Pade-approximant approach can be applied. The variational expressions considered include those for the wave function, for photoionization transition matrix elements, as well as for scattering matrix (K-matrix) elements. We have applied this approach to the 5sigma photoionization of CO using the frozen-core Hartree-Fock and fixed-nuclei approximations. We find that the Pade-approximant method converges rapidly and reliably. Both total photoionization cross sections and photoelectron angular distributions from threshold to 40 eV are presented and compared to previous experimental and theoretical results. We find major quantitative discrepancies between the present results for the total cross section and previous theoretical results.
- Research Organization:
- Department of Chemistry, Princeton University, Princeton, New Jersey 08544
- OSTI ID:
- 5541294
- Journal Information:
- Phys. Rev. A; (United States), Vol. 28:3
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
CARBON MONOXIDE
PHOTOIONIZATION
ELECTRON-MOLECULE COLLISIONS
PADE APPROXIMATION
PHOTON-MOLECULE COLLISIONS
CONVERGENCE
CORRECTIONS
INTEGRAL EQUATIONS
SCATTERING
SCHWINGER VARIATIONAL METHOD
TOTAL CROSS SECTIONS
CARBON COMPOUNDS
CARBON OXIDES
CHALCOGENIDES
COLLISIONS
CROSS SECTIONS
ELECTRON COLLISIONS
EQUATIONS
IONIZATION
MOLECULE COLLISIONS
OXIDES
OXYGEN COMPOUNDS
PHOTON COLLISIONS
VARIATIONAL METHODS
640304* - Atomic
Molecular & Chemical Physics- Collision Phenomena