Accurate Spectral Properties within Double-Hybrid Density Functional Theory: A Spin-Scaled Range-Separated Second-Order Algebraic-Diagrammatic Construction-Based Approach

Our second-order algebraic-diagrammatic construction [ADC(2)]-based double-hybrid (DH) ansatz (J. Chem. Theory Comput. 2019, 15, 4440. DOI: 10.1021/acs.jctc.9b00391) is combined with range-separation techniques. In the present scheme, both the exchange and the correlation contributions are range-separated, while spin-scaling approaches are also applied. The new methods are thoroughly tested for the most popular benchmark sets including 250 singlet and 156 triplet excitations, as well as 80 oscillator strengths. It is demonstrated that the range separation for the correlation contributions is highly recommended for both the genuine and the ADC(2)-based DH approaches. Our results show that the latter scheme slightly but consistently outperforms the former one for single excitation dominated transitions. Furthermore, states with larger fractions of double excitations are assessed as well, and challenging charge-transfer excitations are also discussed, where the recently proposed spin-scaled long-range corrected DHs fail. The suggested iterative fourth-power scaling RS-PBE-P86/SOS-ADC(2) method, using only three adjustable parameters, provides the most robust and accurate excitation energies within the DH theory. In addition, the relative error of the oscillator strengths is reduced by 65% compared to the best genuine DH functionals.

Automated summary

This paper combines second-order algebraic-diagrammatic construction with range-separation techniques to propose a new double-hybrid method. Through testing, it is found that range separation for correlation contributions is highly effective for both the ADC(2)-based DH approaches and the genuine DH approaches.