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.

A Mountaineering Strategy to Excited States: Highly Accurate Energies and Benchmarks for Medium Sized Molecules

Lipparini F.
;
2020-01-01

Abstract

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.
2020
Loos, P. -F.; Lipparini, F.; Boggio-Pasqua, M.; Scemama, A.; Jacquemin, D.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11568/1041024
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