TheoDORE: A toolbox for a detailed and automated analysis of electronic excited state computations

Abstract

The advent of ever more powerful excited-state electronic structure methods has lead to a tremendous increase in the predictive power of computation but it has also rendered the analysis of these computations more and more challenging and time-consuming. TheoDORE tackles this problem through providing tools for post-processing excited-state computations, which automate repetitive tasks and provide rigorous and reproducible descriptors. Interfaces are available for ten different quantum chemistry codes and a range of excited-state methods implemented therein. This article provides an overview of three popular functionalities within TheoDORE, a fragment-based analysis for assigning state character, the computation of exciton sizes for measuring charge transfer, and the natural transition orbitals used not only for visualisation but also for quantifying multiconfigurational character. Using the examples of an organic push-pull chromophore and a transition metal complex, it is shown how these tools can be used for a rigorous and automated assignment of excited-state character. In the case of a conjugated polymer, we venture beyond the limits of the traditional molecular orbital picture to uncover spatial correlation effects using electron-hole correlation plots and conditional densities.

Suppressing dimer formation by increasing conformational freedom in multi-carbazole thermally activated delayed fluorescence emitters

“…However, the trend is not straightforward, as an increasing number of carbazole donors also increases the CT character of the compound. Consequently, 3CzCNPyz has a higher calculated CT number 54 than 2Cz2CNPyz (Table S27). While the calculations do not take into account environmental effects that can influence the measured emission, they help explain the general trend observed.…”

pysisyphus: Exploring potential energy surfaces in ground and excited states

“…pysisyphus allows ES tracking through wavefunction overlap, [38] by transition density matrix overlaps, [36] or by NTO overlaps. [14] Wavefunction overlaps (WFOs) between two sets of electronic states given by the wavefunctions {|Ψ I i} and {|Ψ J i} calculated at molecular geometries r I and r J can be expanded into SDs:…”

Orbital-free photophysical descriptors to predict directional excitations in metal-based photosensitizers

“…The automatized electronic-structure analysis to compute EEDL and SIEL was implemented within the program package TheoDORE. 37 The computational protocol to compute EEDL n and SIEL numbers is described in Section S2 of the ESI. † For each of the [Ru(bpy) 3 ] 2+ compounds 1b–1v , the system was divided into four fragments: the metal center and the three bpy ligands.…”