Validation of double-hybrid density functionals for electric response properties of transition-metal systems: a new...

Double-hybrid density functional approximations are increasingly popular for electronic structure calculations within density functional theory. However, despite much progress in numerous interesting efforts in this respect, further extension of this approach to the chemistry and physics of transition-metal compounds poses major challenges that remain to be addressed. In the present article, without the use of any empirical fitting to experimental or high-level ab initio data, we propose a new parameter-free double-hybrid density functional, called mPWPW91DH, for the electric response properties of transition-metal-containing molecules. It is based on a mixing of modified Perdew-Wang (mPW) and Perdew-Wang91 (PW91) generalized gradient approximations for exchange and correlation, respectively, along with Hartree-Fock (HF) exchange and a perturbative correlation term obtained from the Kohn-Sham orbitals and eigenvalues. The performance of this functional was tested on a number of representative test sets of static dipole polarizabilities and dipole moments of molecules containing transition metals and main-group elements. From our analysis, mPWPW91DH seems to represent a significant improvement in comparison to functionals on the different rungs of Jacob's ladder. Moreover, scrutinizing the role of exchange and correlation and their contributions in the functionals shows evidence of the superiority of this new functional with respect to other parameter-free and parametrized double-hybrid functionals. The results of the present study are encouraging in terms of further improvements in double-hybrid approximations for investigating the response properties of more complex transition-metal systems.