Quantum Chemistry without Wave Functions:  Two-Electron Reduced Density Matrices

For 50 years, progress toward the direct calculation of the ground-state two-electron reduced density matrix (2-RDM) was stymied from an inability to constrain the 2-RDM to represent an N-electron wave function. Recent advances in theory and optimization have realized the direct calculation of the 2-RDM. A variational 2-RDM procedure, using first-order semidefinite programming, has been shown to capture multireference correlation effects important at nonequilibrium geometries Mazziotti, Phys. Rev. Lett. 2004, 93, No. 213001. This method emerged from research on a nonvariational calculation of the 2-RDM by the contracted Schrödinger equation. Both approaches will be discussed and illustrated.