Applications of Time-Dependent and Time-Independent Density Functional Theory to Electronic Transitions in Tetrahedral d(0) Metal Oxides

作者：Seidu Issaka; Krykunov Mykhaylo^*; Ziegler Tom

来源：Journal of Chemical Theory and Computation, 2015, 11(9): 4041-4053.

DOI：10.1021/acs.jctc.5b00298

We present benchmark calculations on excitation energies based on time-dependent density functional theory (TDDFT) as well as orbital relaxed self-consistent and constricted variational DFT (RSCF-CV-DFT) with and without use of the Tamm-Dancoff approximation. The compilation contains results for the 3d complexes MnO4-, CrO42-, and VO43-, as well as the 4d congeners RuO4, TcO4-, and MoO42-, and 5d homologues OsO4, ReO4-, and WO42-. Considerations have been given to the local density approximation (LDA) and the functionals BP86 and PBE based on the generalized gradient approximation (GGA), as well as the hybrids B3LYP, BHLYP, and PBEO and the length corrected functional LCBP86. We find for the 3d complexes that RSCF-CV-DFT fares better than TDDFT. Thus, in the case of RSCF-CV-DFT, the average rootmean-square deviations (RMSDs) are 0.25-0.3 eV for GGAs, 0.1 eV for B3LYP, and 0.45 eV for BHLYP. TDDFT affords RiVISDs that on average range from 0.3 eV for local functionals to 0.7 eV for BHLYP with the largest fraction of Hartree-Fock (HF) exchange. TDDFT is seen to fare better among the heavier tetraoxo systems. For the 4d and 5d systems, the three functionals B3LYP, PBEO with an intermediate fraction of HF exchange, and LCBP86 have the lowest RMSD of 0.2 eV, whereas the local functionals (LDA, BP86, BPE) and BHLYP with the highest HF fraction and LCBP86* have a somewhat larger RMSD of 0.3 eV. Nearly the same performance is observed for RSCF-CV-DFT with respect to the different functionals in the case of the 4d and 5d systems. Thus, for the heavier tetraoxo systems, the two DFT schemes are comparable in accuracy.

• 出版日期2015-9