Double Hybrid Density Functionals for the Electronic Excitation Energies of Linear Cyanines.

Abstract

The lowest bright electronic excitations of seven model linear cyanines (CN3-CN15) using 28 double-hybrid (DH) density functionals are benchmarked against accurate and recent CC3 results. Some of these DH functionals are recently designed specifically for excited electronic state calculations. In addition, CIS, CIS(D), SCS-CIS(D), and SOS-CIS(D) were also tested. Four different basis sets were used for the vertical electronic excitation calculations: cc-pVDZ, aug-cc-pVDZ, cc-pVTZ, and aug-cc-pVTZ basis. Augmented basis sets (e.g. aug-cc-pVDZ and aug-cc-pVTZ) are found to be required for accurate and consistent results using DH functionals. The DH functionals tested in this work are classified into four main groups: global double-hybrids (GDH), range-separated double-hybrids (RSDH), spin-component and spin-opposite scaling global double-hybrids (SCS/SOS-GDH), and spin-component and spin-opposite scaling range-separated double-hybrids (SCS/SOS-RSDH). Within these groups, the SCS/SOS-RSDH group of functionals is found to provide the lowest mean absolute error (MAE) values (in the range 0.020-0.148 eV) in comparison with the GDH group (0.195-0.441 eV), the RSDH group (0.186-0.511 eV), and the SCS/SOS-GDH group (0.079-0.461 eV). Of all the DH functionals and ab initio methods investigated in the present contribution, the following functionals are found to be the most accurate and consistent: SCS-ωB2GPPLYP (MAE = 0.036 eV), SOS-ωB2GPPLYP (MAE = 0.020 eV), SOS-ωB88PP86 (MAE = 0.035 eV), and SOS-ωPBEPP86 (MAE = 0.037 eV). In general, the ab initio methods tested here show mediocre performance as compared to many DH functionals.