A dual-level approach to four-component relativistic density-functional theory

• Published in: Chemical physics letters Vol. 508; no. 1-3; pp. 177 - 181
• Main Authors: Mizukami, Wataru, Nakajima, Takahito, Hirao, Kimihiko, Yanai, Takeshi
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 18.05.2011
• ISSN: 0009-2614; 1873-4448
• DOI: 10.1016/j.cplett.2011.04.031

[Display omitted] ► A convenient method incorporating the higher-order relativistic and basis-set effects. ► A connection between low-cost two-component and expensive four-component calculations. ► Accelerates four-component relativistic DFT calculations. An efficient approach to the fully relativistic density-functional theory (DFT) is proposed to accelerate Dirac–Kohn–Sham calculation that uses high-quality basis sets and hybrid exchange–correlation functional. The dual-level approach proposed by Nakajima and Hirao underlies the present method, estimating high-level four-component DFT energy perturbatively from reference density matrix, which is determined by a relatively inexpensive self-consistent calculation using low-quality basis sets and low-cost functional. A further approximation based on Infinite-Order Two-Component relativistic Hamiltonian is incorporated into the low-level treatment. Accuracy and efficiency were examined by benchmark calculation of spectroscopic values for MH, M2 (M=Cu, Ag, and Au), and AtH.