In this work, we assess the accuracy of the Bethe-Salpeter equation (BSE) many-body Green's function formalism, adopting the eigenvalue-self-consistent ev exchange-correlation kernel, for the calculation of the excited-state () and excess dipole moments (Δ), 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/ev 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 and Δ. For DMABN our results show that BSE/ev provides Δ values closer to the CCSD reference and more consistent trends than TD-DFT. Moreover, a statistical analysis of both Δ and for the set of 25 dyes shows that the BSE/ev accuracy is comparable or sometimes slightly better than that of TD-M06-2X and TD-CAM-B3LYP, BSE/ev outperforming TD-DFT in challenging cases (zwitterionic and cyanine transitions). Finally, the starting point dependency of BSE/ev seems to be larger for Δ, ES dipoles, and oscillator strengths than for transition energies.

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http://dx.doi.org/10.1039/d3cp04467jDOI Listing

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