Geometric Constraints on Two-electron Reduced Density Matrices

Abstract: For many-electron systems, the second-order reduced density matrix (2-RDM) provides sufficient information for characterizing their properties of interests in physics and chemistry, ranging from total energy, magnetism, quantum correlation and entanglement to long-range orders. Theoretical prediction of the structural properties of 2-RDM is an essential endeavor in quantum chemistry, condensed matter physics and, more recently, in quantum computation. Since 1960s, enormous progresses have been made in developing RDM-based electronic structure theories and their large-scale computational applications in predicting molecular structure and mechanical, electrical and optical properties of various materials. However, for strongly correlated systems, such as high-temperature superconductors, transition-metal-based biological catalysts and complex chemical bonds near dissociation limit, accurate approximation is still out of reach by currently most sophisticated approaches. This limitation highlights the elusive structural feature of 2-RDM that determines quantum correlation in many-electron system. Here, we present a set of constraints on 2-RDM based on the basic geometric property of Hilbert space and the commutation relations of operators. Numerical examples are provided to demonstrate the pronounced violation of these constraints by the variational 2-RDMs. It is shown that, for a strongly correlated model system, the constraint violation may be responsible for a considerable portion of the variational error in ground state energy. Our findings provide new insights into the structural subtlety of many-electron 2-RDMs.