Excess and excited-state dipole moments of real-life dyes: a comparison between wave-function, BSE/GW, and TD-DFT values

In this work, we assess the accuracy of the Bethe-Salpeter equation (BSE) many-body Green's function formalism, adopting the eigenvalue-self-consistent evGW exchange-correlation kernel, for the calculation of the excited-state (mu(ES)) and excess dipole moments (Delta mu), the latter ones being the changes of dipole amplitude between the ground and excited states (ES), in organic dyes. We compare the results obtained with wave-function methods [ADC(2), CC2, and CCSD], time-dependent density functional theory (TD-DFT), and BSE/evGW levels of theory. First, we compute the evolution of the dipole moments of the two lowest singlet excited states of 4-(dimethylamino)benzonitrile (DMABN) upon twisting of the amino group. Next, we use a set of 25 dyes having ES characters ranging from locally excited to charge transfer to determine both mu(ES) and Delta mu. For DMABN our results show that BSE/evGW provides Delta mu values closer to the CCSD reference and more consistent trends than TD-DFT. Moreover, a statistical analysis of both Delta mu and mu(ES) for the set of 25 dyes shows that the BSE/evGW accuracy is comparable or sometimes slightly better than that of TD-M06-2X and TD-CAM-B3LYP, BSE/evGW outperforming TD-DFT in challenging cases (zwitterionic and cyanine transitions). Finally, the starting point dependency of BSE/evGW seems to be larger for Delta mu, ES dipoles, and oscillator strengths than for transition energies.

Automated summary

In this study, the accuracy of BSE/evGW method for the calculation of excited state and excess dipole moments in organic dyes is assessed and compared with other methods. The results demonstrate that BSE/evGW method exhibits higher accuracy in calculating excess dipole moments of dyes and outperforms other methods in certain cases.