2018/07/02 by Pierre-François Loos, Pierre‐François Loos, Anthony Scemama +4 · 373 citations
Chemistry · Engineering · Physics and Astronomy · #Acetylene #Advanced Chemical Physics Studies #Atomic orbital #Atomic physics #Basis set #Catalysis #Chemistry #Computational chemistry #Configuration interaction #Coupled cluster #Density functional theory #Electron #Excited state #Molecular Junctions and Nanostructures #Molecule #Organic chemistry #Photochemistry and Electron Transfer Studies #Physics #Transition state #Valence (chemistry) #physics.chem-ph #physics.comp-ph
paper · pdf · doi:10.1021/acs.jctc.8b00406
published in Journal of Chemical Theory and Computation 14(8), 4360-4379 (American Chemical Society) · 57 pages, 2 figures
openalex publication_date 2018/07/02 · arxiv created 2018/07/05 · arxiv updated 2019/05/06 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/06
Striving to define very accurate vertical transition energies, we perform both high-level coupled cluster (CC) calculations (up to CCSDTQP) and selected configuration interaction (sCI) calculations (up to several millions of determinants) for 18 small compounds (water, hydrogen sulfide, ammonia, hydrogen chloride, dinitrogen, carbon monoxide, acetylene, ethylene, formaldehyde, methanimine, thioformaldehyde, acetaldehyde, cyclopropene, diazomethane, formamide, ketene, nitrosomethane, and the smallest streptocyanine). By systematically increasing the order of the CC expansion, the number of determinants in the CI expansion as well as the size of the one-electron basis set, we have been able to reach near full CI (FCI) quality transition energies. These calculations are carried out on CC3/ aug -cc-pVTZ geometries, using a series of increasingly large atomic basis sets systematically including diffuse functions. In this way, we define a list of 110 transition energies for states of various characters (valence, Rydberg, n → π *, π → π*, singlet, triplet, etc.) to be used as references for further calculations. Benchmark transition energies are provided at the aug -cc-pVTZ level as well as with additional basis set corrections, in order to obtain results close to the complete basis set limit. These reference data are used to benchmark a series of 12 excited-state wave function methods accounting for double and triple contributions, namely ADC(2), ADC(3), CIS(D), CIS(D ∞ ), CC2, STEOM-CCSD, CCSD, CCSDR(3), CCSDT-3, CC3, CCSDT., and CCSDTQ. It turns out that CCSDTQ yields a negligible difference with the extrapolated CI values with a mean absolute error as small as 0.01 eV, whereas the coupled cluster approaches including iterative triples are also very accurate (mean absolute error of 0.03 eV). Consequently, CCSDT-3 and CC3 can be used to define reliable benchmarks. This observation does not hold for ADC(3) that delivers quite large errors for this set of small compounds, with a clear tendency to overcorrect its second-order version, ADC(2). Finally, we discuss the possibility to use basis set extrapolation approaches so as to tackle more easily larger compounds.