A general nonlinear expansion form for electronic wave functions.
A new expansion form is presented for electronic wave functions. The wave function is a linear combination of product basis functions, and each product basis function in turn is formally equivalent to a linear combination of configuration state functions that comprise an underlying linear expansion space. The expansion coefficients that define the basis functions are nonlinear functions of a smaller number of variables. The expansion form is appropriate for both ground and excited states and to both closed and open shell molecules. The method is formulated in terms of spin-eigenfunctions using the graphical unitary group approach (GUGA), and consequently it does not suffer from spin contamination.
Shepard
Ron
R
Chemistry Division, Argonne National Laboratory, Argonne, Illinois 60439, USA. shepard@tcg.anl.gov