Assessment of State-Averaged Driven Similarity Renormalization Group on Vertical Excitation Energies: Optimal Flow Parameters and Applications to Nucleobases

We present a comprehensive excited-state benchmark for the state-averaged (SA) driven similarity renormalization group (DSRG) [Li, C.; Evangelista, F. A. J. Chem. Phys. 2018, 148, 124106]. Following the QUEST database [Veril, M.; Scemama, A.; Caffarel, M.; Lipparini, F.; Boggio-Pasqua, M.; Jacquemin, D.; Loos, P.-F. Wiley Interdiscip. Rev. Comput. Mol. Sci. 2021, 11, e1517], 280 vertical transition energies of 35 medium-sized molecules are computed using the SA-DSRG derived second-and third-order perturbation theories (PT2/PT3) along with a nonperturbative approach [sq-LDSRG(2)]. Comparing to the theoretical best estimates, the optimal flow parameter is found to be 0.35 and 2.0 Eh 2 for SA-DSRG-PT2 and SA-DSRG-PT3, respectively. For SA-sq-LDSRG(2), a flow parameter of 1.5 Eh 2 provides converged equations without compromising the accuracy. We then assess the accuracy of the SA-DSRG hierarchy using these parameters. The SA-DSRG-PT2 scheme outperforms the level-shifted CASPT2 by 0.10 eV in mean absolute error (MAE), yet this accuracy is slightly inferior than that of CASPT2 with the ionization-potential-electron-affinity shift. Both SA-DSRG-PT3 and SA-sq-LDSRG(2) yield a MAE of 0.10 eV, which is comparable to that of CASPT3 (0.09 eV). Finally, we compute vertical excitation energies of several low-lying singlet states of nucleobases. The SA-sq-LDSRG(2) approach provides highly accurate results for pi-* pi* excitations, while n-* pi* transitions are better described by SA-DSRG-PT3.

Automated summary

In this study, the state-averaged driven similarity renormalization group (SA-DSRG) method was used to compute the vertical transition energies of 280 molecules. The optimal parameters were found and compared with other theoretical methods. The accuracy of SA-DSRG-PT2 was found to be better than level-shifted CASPT2, while SA-DSRG-PT3 and SA-sq-LDSRG(2) were comparable to CASPT3. Additionally, the vertical excitation energies of nucleobases were calculated, with SA-sq-LDSRG(2) performing well for π-* π* excitations and SA-DSRG-PT3 for n-* π* transitions.