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dc.contributor.authorStaroverov, Viktor N.en_US
dc.date.accessioned2009-05-19T17:38:51Z
dc.date.available2009-05-19T17:38:51Z
dc.date.issued1997-05-19T17:38:51Z
dc.identifier.urihttp://hdl.handle.net/10464/1172
dc.description.abstractAll-electron partitioning of wave functions into products ^core^vai of core and valence parts in orbital space results in the loss of core-valence antisymmetry, uncorrelation of motion of core and valence electrons, and core-valence overlap. These effects are studied with the variational Monte Carlo method using appropriately designed wave functions for the first-row atoms and positive ions. It is shown that the loss of antisymmetry with respect to interchange of core and valence electrons is a dominant effect which increases rapidly through the row, while the effect of core-valence uncorrelation is generally smaller. Orthogonality of the core and valence parts partially substitutes the exclusion principle and is absolutely necessary for meaningful calculations with partitioned wave functions. Core-valence overlap may lead to nonsensical values of the total energy. It has been found that even relatively crude core-valence partitioned wave functions generally can estimate ionization potentials with better accuracy than that of the traditional, non-partitioned ones, provided that they achieve maximum separation (independence) of core and valence shells accompanied by high internal flexibility of ^core and Wvai- Our best core-valence partitioned wave function of that kind estimates the IP's with an accuracy comparable to the most accurate theoretical determinations in the literature.en_US
dc.language.isoengen_US
dc.publisherBrock Universityen_US
dc.subjectValence (Theoretical chemistry)en_US
dc.subjectAtomic structure.en_US
dc.subjectMonte Carlo method.en_US
dc.titleVariational Monte Carlo study of core-valence separation schemes for first-row atoms and positive ions /en_US
dc.typeElectronic Thesis or Dissertationen_US
dc.degree.nameM.Sc. Chemistryen_US
dc.degree.levelMastersen_US
dc.contributor.departmentDepartment of Chemistryen_US
dc.degree.disciplineFaculty of Mathematics and Scienceen_US


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