New optimally tuned range-separated models are proposed for describing the excited-states characteristics of experimentally known and theoretically designed compounds in electrically pumped organic semiconductor laser diodes.

We propose and validate several variants of the optimally tuned range-separated hybrid functionals (OT-RSHs) including different density functional approximations for predicting the fluorescence lifetimes of different categories of fluorophores within the time-dependent density functional theory (TD-DFT) framework using both the polarizable continuum and state-specific solvation models. Our main idea originates from performing the optimal tuning in the presence of a contribution of the exact-like exchange at the short-range part, which, in turn, leads to the small values of the range-separation parameter, and computing the fluorescence lifetimes using the models including no or small portions of the short-range exact-like exchange. Particular attention is also paid to the influence of the geometries of emitters on fluorescence lifetime computations. It is shown that our developed OT-RSHs along with the polarizable continuum model can be considered as the promising candidates within the TD-DFT framework for the prediction of fluorescence lifetimes for various fluorophores. We find that the proposed models not only outperform their standard counterparts but also provide reliable data better than or comparable to the conventional hybrid functionals with both the fixed and interelectronic distance-dependent exact-like exchanges. Furthermore, it is also revealed that when the excited state geometries come into play, more accurate descriptions of the fluorescence lifetimes can be achieved. Hopefully, our findings can give impetus for future developments of OT-RSHs for computational modeling of other characteristics in fluorescence spectroscopy as well as for verification of the related experimental observations.

Concerning the major factors in the context of excited states analyses, namely charge centroids of the orbitals involved in the excitations, the distance between orbital centroids, and overlap integrals, a new metric-the Ω index-is proposed to assign the character and optical properties of electronically excited states. Using several molecules from different classes and also a well-studied standard database for time-dependent density functional theory (TD-DFT) studies as benchmark criteria, accountability of the developed index is numerically assessed for local, charge transfer, and Rydberg excitations. It is shown that the nature of excited states can be discriminated using the Ω index, where its superior performance for those situations in which the previous descriptors were not helpful is also unveiled. Relationships are also examined between the Ω index and optical properties of some molecules under study in the framework of the sum-over-state approach. It is observed that there are correlations between the proposed index and computed hyperpolarizabilities based on the sum-over-state scheme. These findings offer the possibility of estimating excited-state properties of large systems from simple descriptors without explicitly performing calculations of high-order response functions.