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4 Two-Component Methods

The four-component wavefunctions of the Dirac-Hartee-Fock method present a practical barrier for the quantum chemical investigator. Methods which decouple the positronic and electronic solutions have been employed with a great deal of success. Though it is not possible to exactly separate the two halves of the DHF solutions for molecular wavefunctions, methods such as the Foldy-Wouthoysen transformation and the related Douglas-Kroll transformation can produce a molecular Hamiltonian which is decoupled to a certain order in the fine structure constant, . The resultant Hamiltonians, and their two component solutions, restore the traditional, familiar picture of molecular electronic structure where all interactions are solely among electrons and nuclei. This return to the two component picture also brings the advantage of dramatically increased affordability of correlated methods.





This document is copyright 1996,
Thu May 29 08:12:02 EDT 1997