Excited-state absorption in tetrapyridyl porphyrins: comparing real-time and quadratic-response time-dependent density functional theory

Three meso-substituted tetrapyridyl porphyrins (free base, Ni(II), and Cu(II)) were investigated for their optical limiting (OL) capabilities using real-time (RT-), linear-response (LR-), and quadratic-response (QR-) time-dependent density functional theory (TDDFT) methods. These species are experimentally known to display a prominent reverse saturable absorption feature between the Q and B bands of the ground-state absorption (GSA), which has been attributed to increased excited-state absorption (ESA) relative to GSA. A recently developed RT-TDDFT based method for calculating ESA from a LR-TDDFT density was utilized with eight exchange-correlation functionals (BLYP, PBE, B3LYP, CAM-B3LYP, PBE0, M06, BHLYP, and BHandH) and contrasted with calculations of ESA using QR-TDDFT with five exchange-correlation functionals (BLYP, B3LYP, CAM-B3LYP, BHLYP, and BHandH). This allowed for comparison between functionals with varying amounts o f exact exchange as well as between the ability o f RT-TDDFT and QR-TDDFT to reproduce OL behavior in porphyrin systems. The absorption peak positions and intensities for GSA and ESA are significantly impacted by the choice o f DFT functional, with the most critical factor identified as the amount of exact exchange in the functional form. Calculating ESA with QR-TDDFT is found to be significantly more sensitive to the amount o f exact exchange than GSA and ESA with RT-TDDFT, as well as GSA with LR-TDDFT. An analogous behavior is also demonstrated for the polycyclic aromatic hydrocarbon coronene. This is problematic when using the same approximate functional for calculation of both GSA and ESA, as the LR- and QR-TDDFT excitation energies will not have similar errors. Overall, the RT-TDDFT method with hybrid functionals reproduces the OL features for the porphyrin systems studied here and is a viable computational approach for efficient screening o f molecular complexes for OL properties.