A Mountaineering Strategy to Excited States: Highly Accurate Energies and Benchmarks for Bicyclic Systems.

Abstract

Pursuing our efforts to define highly accurate estimates of the relative energies of excited states in organic molecules, we investigate, with coupled-cluster methods including iterative triples (CC3 and CCSDT), the vertical excitation energies of 10 bicyclic molecules (azulene, benzoxadiazole, benzothiadiazole, diketopyrrolopyrrole, furofuran, phthalazine, pyrrolopyrrole, quinoxaline, tetrathiafulvalene, and thienothiophene). In total, we provide aug-cc-pVTZ reference vertical excitation energies for 91 excited states of these relatively large systems. We use these reference values to benchmark various wave function methods, i.e., CIS(D), EOM-MP2, CC2, CCSD, STEOM-CCSD, CCSD(T)(a)*, CCSDR(3), CCSDT-3, ADC(2), ADC(2.5), and ADC(3), as well as some spin-scaled variants of both CC2 and ADC(2). These results are compared to those obtained previously on smaller molecules. It turns out that while the accuracy of some methods is almost unaffected by system size, e.g., CIS(D) and CC3, the performance of others can significantly deteriorate as the systems grow, e.g., EOM-MP2 and CCSD, whereas others, e.g., ADC(2) and CC2, become more accurate for larger derivatives.