Realization of quantum chemistry without wave functions through first-order semidefinite programming.
Determining the energy and properties of an N-electron molecule through a two-electron variational optimization has been a dream for more than half a century. While optimizations, using two-electron reduced density matrices constrained to represent N electrons, have recently been achieved, the computational costs are prohibitive. In this report an efficient algorithm with an order-of-magnitude reduction in floating-point operations and memory usage is presented. Because the optimization occurs on the space of two electrons, this method automatically treats strong, multireference correlation. Application is made to N2 and H6 where the method yields consistent accuracy at all geometries.
Mazziotti
David A
DA
Department of Chemistry, James Franck Institute, The University of Chicago, Chicago, Illinois 60637, USA. damazz@uchicago.edu