Orbital angular momentum constraints in the variational optimization of the two-electron reduced-density matrix

摘要

The direct variational determination of the two-electron reduced-density matrix (2-RDM) corresponding to an atomic or molecular system is usually carried out in a basis of real-valued atom-centered Gaussian basis functions, under the assumption that the 2-RDM is a real-valued quantity. However, for systems that possess orbital angular momentum symmetry, the description of states with a well-defined, nonzero z projection of the orbital angular momentum requires a computational framework generalized to include either complex basis functions or a complex-valued 2-RDM. We consider a semidefinite program suitable for the direct optimization of a complex-valued 2-RDM and explore the role of orbital angular momentum constraints in systems that possess the relevant symmetries. For atomic systems, constraints on the expectation values of the square and z projection of the orbital angular momentum operator allow one to optimize 2-RDMs for multiple orbital angular momentum states. Similarly, in linear molecules, orbital angular momentum projection constraints enable the description of multiple electronic states and, moreover, the application of such constraints is essential for a qualitatively correct description of the electronic structure. For example, in the case of molecular oxygen, we demonstrate that orbital angular momentum constraints are necessary to recover the correct energy ordering of the lowest-energy singlet and triplet states near the equilibrium geometry. However, care must still be taken in the description of the dissociation limit, because the 2-RDM-based approach is not size consistent, and the sizeconsistency error varies dramatically, depending on the z projections of the spin and orbital angular momenta.