期刊
JOURNAL OF CHEMICAL PHYSICS
卷 155, 期 4, 页码 -出版社
AIP Publishing
DOI: 10.1063/5.0057957
关键词
-
资金
- European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program [810367]
This work presents a self-consistent extension of a density-based basis-set correction method for wave function electronic-structure calculations. The study shows that the self-consistent approach allows for lowering total energy and changing wave functions under the effect of basis-set correction, leading to improved dipole moments. The research confirms the validity of the density-based basis-set correction scheme.
This work provides a self-consistent extension of the recently proposed density-based basis-set correction method for wave function electronic-structure calculations [E. Giner et al., J. Chem. Phys. 149, 194301 (2018)]. In contrast to the previously used approximation where the basis-set correction density functional was a posteriori added to the energy from a wave-function calculation, here the energy minimization is performed including the basis-set correction. Compared to the non-self-consistent approximation, this allows one to lower the total energy and change the wave function under the effect of the basis-set correction. This work addresses two main questions: (i) What is the change in total energy compared to the non-self-consistent approximation and (ii) can we obtain better properties, namely, dipole moments, with the basis-set corrected wave functions. We implement the present formalism with two different basis-set correction functionals and test it on different molecular systems. The main results of the study are that (i) the total energy lowering obtained by the self-consistent approach is extremely small, which justifies the use of the non-self-consistent approximation, and (ii) the dipole moments obtained from the basis-set corrected wave functions are improved, being already close to their complete basis-set values with triple-zeta basis sets. Thus, the present study further confirms the soundness of the density-based basis-set correction scheme. Published under an exclusive license by AIP Publishing.
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