Analysis of two overlapping fragmentation approaches in density matrix construction: GMBE-DM vs. ADMA

Abstract

In this study, we conduct a comparative analysis of two density matrix construction methods: the generalized many-body expansion for building density matrices (GMBE-DM) based on the set-theoretical principle of inclusion/exclusion and the adjustable density matrix assembler (ADMA) based on the Mulliken–Mezey ansatz. We apply these methods to various noncovalent clusters, including water clusters, ion–water clusters, and ion-pair clusters, using both small 6-31G(d) and large def2-TZVPPD basis sets. Our findings reveal that the GMBE-DM method, particularly when combined with the purification scheme and truncation at the one-body level [GMBE(1)-DM-P], exhibits superior performance across all test systems and basis sets. In contrast, all ADMA set of methods show reasonable results only with small and compact basis sets. For example, GMBE(1)-DM-P outperforms the best ADMA method by at least 4 and 16 times with small and large basis sets, respectively, in the case of (H₂O)_N=6–55. This highlights the significance of the basis set choice for ADMA, which is even more critical than the fragmentation scheme, such as the size of subsystems, while GMBE-DM consistently produces accurate results irrespective of the chosen basis set. Consequently, the efficient and robust GMBE(1)-DM-P approach is recommended as a fragmentation method for generating accurate absolute and relative energies across different binding patterns and basis sets for noncovalent clusters.