Assessment of local coupled cluster methods for excited states of BODIPY/Aza‐BODIPY families

摘要: It was previously reported that Laplace transformed local CC2 (LCC2*) provided the best agreement (MAE = 0.145 eV) when comparing vertical excitation energies to experimental λmax for a benchmark set of 17 BODIPY/Aza-BODIPY molecules. However, these did not agree with values obtained from canonical CC2. Here we report LCC2* computations on same molecules using newly implemented treatment ground state. Comparison resolution-of-identity approximate coupled cluster second-order (RI-CC2) results demonstrate new quantitatively. Furthermore, can easily be corrected empirically also provide excellent experiment. We show algebraic diagrammatic construction (LADC(2)) method exhibits differences between implementations as seen LCC2. The source difference is traced an improved state in methods, which decreases experiment (as attributed fortuitous cancellation errors) but significantly improves RI-CC2. While absolute now larger deviations, there remains strong linear correlation and For are determined DLPNO-STEOM-CCSD shown have 0.145 eV), all single-reference methods. LCC2*, RI-CC2 series eight large BODIPYs Aza-BODIPYs.