Handling Ensemble N-Representability Constraint in Explicit-by-Implicit Manner.

Abstract

The convergence issues caused by the improper treatment of the ensemble N-representability constraint have severely affected the applicability and reproducibility of reduced density matrix functional theory (RDMFT). Unlike the commonly used Lagrange methods explicitly bringing the constraint into the objective functions, we present a different idea to handle the constraint in an implicit manner, which is achieved by introducing implicit functions to exactly consider the nonlinear unclear connection embedded in the explicit constraint. This explicit-by-implicit idea, denoted as EBI, thus transforms the constrained optimization problem into an unconstrained minimization problem. The tests on different systems, initial guesses, and functionals demonstrate the superiority of EBI in the treatment of the ensemble N-representability constraint. Therefore, EBI solves the convergence issues of the Lagrange methods, which is essential for further development and application of RDMFT. Besides, the idea of EBI is helpful for the treatment of different constrained problems in modern physics and chemistry.