2019/12/31 by Pierre-François Loos, Pierre‐François Loos, Filippo Lipparini +4 · 237 citations
Chemistry · Earth and Planetary Sciences · Physics and Astronomy · #Advanced Chemical Physics Studies #Atmospheric Ozone and Climate #Atomic physics #Chemistry #Coupled cluster #Dipole #Excitation #Excited state #Ground state #Ionization #Molecule #Perturbation theory (quantum mechanics) #Photochemistry and Electron Transfer Studies #Physics #Quantum mechanics #Rydberg formula #Singlet state #Valence (chemistry) #physics.chem-ph #physics.comp-ph
paper · pdf · doi:10.1021/acs.jctc.9b01216
published in Journal of Chemical Theory and Computation 16(3), 1711-1741 (American Chemical Society) · 78 pages, 2 figures (supporting information available)
openalex publication_date 2020/01/27 · arxiv created 2020/01/31 · arxiv updated 2020/06/05 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/05
Following our previous work focusing on compounds containing up to 3 non-hydrogen atoms [ J. Chem. Theory Comput. 2018, 14, 4360–4379], we present here highly accurate vertical transition energies obtained for 27 molecules encompassing 4, 5, and 6 non-hydrogen atoms: acetone, acrolein, benzene, butadiene, cyanoacetylene, cyanoformaldehyde, cyanogen, cyclopentadiene, cyclopropenone, cyclopropenethione, diacetylene, furan, glyoxal, imidazole, isobutene, methylenecyclopropene, propynal, pyrazine, pyridazine, pyridine, pyrimidine, pyrrole, tetrazine, thioacetone, thiophene, thiopropynal, and triazine. To obtain these energies, we use equation-of-motion/linear-response coupled cluster theory up to the highest technically possible excitation order for these systems (CC3, EOM-CCSDT, and EOM-CCSDTQ) and selected configuration interaction (SCI) calculations (with tens of millions of determinants in the reference space), as well as the multiconfigurational n -electron valence state perturbation theory (NEVPT2) method. All these approaches are applied in combination with diffuse-containing atomic basis sets. For all transitions, we report at least CC3/ aug -cc-pVQZ vertical excitation energies as well as CC3/ aug -cc-pVTZ oscillator strengths for each dipole-allowed transition. We show that CC3 almost systematically delivers transition energies in agreement with higher-level methods with a typical deviation of ±0.04 eV, except for transitions with a dominant double excitation character where the error is much larger. The present contribution gathers a large, diverse, and accurate set of more than 200 highly accurate transition energies for states of various natures (valence, Rydberg, singlet, triplet, n → π*, π → π*, ...). We use this series of theoretical best estimates to benchmark a series of popular methods for excited state calculations: CIS(D), ADC(2), CC2, STEOM-CCSD, EOM-CCSD, CCSDR(3), CCSDT-3, CC3, and NEVPT2. The results of these benchmarks are compared to the available literature data.