Benchmarking two-photon absorption strengths of rhodopsin chromophore models with CC3 and CCSD methodologies: An assessment of popular density functional approximations

Abstract

This work presents the investigations of the impact of an increasing electron correlation in the hierarchy of coupled-cluster methods, i.e., CC2, CCSD, and CC3, on two-photon absorption (2PA) strengths for the lowest excited state of the minimal rhodopsin’s chromophore model—cis-penta-2,4-dieniminium cation (PSB3). For a larger chromophore’s model [4-cis-hepta-2,4,6-trieniminium cation (PSB4)], CC2 and CCSD calculations of 2PA strengths were performed. Additionally, 2PA strengths predicted by some popular density functional theory (DFT) functionals differing in HF exchange contribution were assessed against the reference CC3/CCSD data. For PSB3, the accuracy of 2PA strengths increases in the following order: CC2 < CCSD < CC3, with the CC2 deviation from both higher-level methods exceeding 10% at 6-31+G* basis sets and 2% at aug-cc-pVDZ basis set. However, for PSB4, this trend is reversed and CC2-based 2PA strength is larger than the corresponding CCSD value. Among the DFT functionals investigated, CAM-B3LYP and BHandHLYP provide 2PA strengths in best compliance with reference data, however, with the error approaching an order of magnitude.