Principal Domains in Local Correlation Theory.

The computational efficiency of local correlation methods is strongly dependent on the size of the domain of functions used to expand local correlating orbitals such as orbital specific or pair natural orbitals. Here, we define a principal domain of order m as the subset of m one-particle functions that provides the best support for a given n-electron wave function by maximizing the partial trace of the one-body reduced density matrix. Principal domains maximize the overlap between the wave function and its approximant for two-electron systems and are the domain selection equivalent of Löwdin's natural orbitals. We present an efficient linear scaling greedy algorithm for obtaining principal domains of projected atomic orbitals and demonstrate its utility in the context of the pair natural orbital local correlation theory. We numerically determine thresholds such that the projected atomic orbital domain error is an order of magnitude smaller than the pair natural orbital truncation error.