Pure State v-Representability of Density Matrix Embedding Theory.

Abstract

Density matrix embedding theory (DMET) formally requires the matching of density matrix blocks obtained from high-level and low-level theories, but this is sometimes not achievable in practical calculations. In such a case, the global band gap of the low-level theory vanishes, and this can require additional numerical considerations. We find that both the violation of the exact matching condition and the vanishing low-level gap are related to the assumption that the high-level density matrix blocks are noninteracting pure-state v-representable (NI-PS-V), which assumes that the low-level density matrix is constructed following the Aufbau principle. To relax the NI-PS-V condition, we develop an augmented Lagrangian method to match the density matrix blocks without referring to the Aufbau principle. Numerical results for the 2D Hubbard and hydrogen model systems indicate that, in some challenging scenarios, the relaxation of the Aufbau principle directly leads to exact matching of the density matrix blocks, which also yields improved accuracy.