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

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 (HO). 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.