American Chemical Society
ct8b00350_si_003.pdb (272.27 kB)

Dual Basis Set Approach for Density Functional and Wave Function Embedding Schemes

Download (272.27 kB)
posted on 2018-07-26, 00:00 authored by Bence Hégely, Péter R. Nagy, Mihály Kállay
A dual basis (DB) approach is proposed which is suitable for the reduction of the computational expenses of the Hartree–Fock, Kohn–Sham, and wave function-based correlation methods. The approach is closely related to the DB approximation of Head-Gordon and co-workers [J. Chem. Phys. 2006, 125, 074108] but specifically designed for embedding calculations. The new approach is applied to our variant of the projector-based embedding theory utilizing the Huzinaga-equation, multilevel local correlation methods, and combined density functional-multilevel local correlation approximations. The performance of the resulting DB density functional and wave function embedding methods is evaluated in extensive benchmark calculations and also compared to that of the corresponding embedding schemes exploiting the mixed-basis approximation. Our results show that, with an appropriate combination of basis sets, the DB approach significantly speeds up the embedding calculations, and, for chemical processes where the electronic structure considerably changes, it is clearly superior to the mixed-basis approximation. The results also demonstrate that the DB approach, if integrated with the mixed-basis approximation, efficiently eliminates the major weakness of the latter, and the combination of the DB and mixed-basis schemes is the most efficient strategy to accelerate embedding calculations.