Construction of a Range-Separated Dual-Hybrid Direct Random Phase Approximation

• Published in: Journal of chemical theory and computation Vol. 15; no. 12; pp. 6678 - 6687
• Main Authors: Mezei, Pál D, Kállay, Mihály
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 10.12.2019
• Subjects: Approximation; Atomizing; Electron gas; Mathematical analysis; Perturbation theory; Polarization (spin alignment); Transition metals
• ISSN: 1549-9618; 1549-9626
• DOI: 10.1021/acs.jctc.9b00891

Blending the good performance of the global hybrid PBE0 functional at short-range and the dual-hybrid dRPA75 functional at long range, we propose a new range-separated direct random phase approximation (dRPA75rs), which considerably improves on the accuracy of the calculated reaction energies and barrier heights compared to the parent approaches and provides a good description of noncovalent interactions without any dispersion correction. We also combine the new scheme with spin-component scaling (SCS-dRPA75rs), which enables the accurate calculation of energy differences for processes involving electron pair breaking, such as atomization. The new method scaling as the fourth power of the system size shows a balanced performance on a broad test set involving radicals, transition metal atoms, and heavy atoms, which makes it competitive with the best double-hybrid functionals based on the second-order perturbation theory. According to the results for the homogeneous electron gas, our dRPA75rs method expectedly gives errors for metallic systems similar to the dRPA approach with an additional error cancellation in the case of partial spin polarization.