The presence of a Rashba band-splitting mechanism mediated by spin-orbit coupling and breaking of inversion symmetry has been suggested as a possible cause for the reduced recombination rates observed in organohalide perovskites. Here, we investigate the interplay of electronic and nuclear degrees of freedom in defining the Rashba splitting in realistic MAPbI3 models. Our simulations disclose a "dynamical Rashba effect", allowing for a quantification of its magnitude under thermal conditions. We find that even in globally centrosymmetric structures the dynamics of the coupled inorganic-organic degrees of freedom give rise to a spatially local Rashba effect which fluctuates on the subpicosecond time scale typical of the methylammonium cation dynamics. This effect is progressively quenched in globally centrosymmetric structures, likely representing the MAPbI3 perovskite at room temperature, on increasing the probed spatial scale up to 32 MAPbI3 units (∼3 nm size) because of the incoherent nuclear thermal motion mediated by the disorder of the organic cations.

Herein, we report a homoleptic iron complex bearing tridentate bis‐carbene (CNC) ligands designed for sensitization of TiO2 photoanodes. Its excited state has been characterized by ultra‐fast transient spectroscopy and time‐dependent density functional theory (TD‐DFT) computations, which reveal a record triplet metal‐to‐ligand charge‐transfer (3MLCT) excited‐state lifetime (16 ps). The new dye was efficiently chemisorbed on TiO2 and promoted electron injection and photocurrent generation in a dye‐sensitized solar cell upon solar irradiation.

Herein we report the synthesis and time-resolved spectroscopic characterization of a homoleptic Fe(ii) complex exhibiting a record (3)MLCT lifetime of 26 ps promoted by benzimidazolylidene-based ligands. Time dependent density functional molecular modeling of the triplet excited state manifold clearly reveals that, at equilibrium geometries, the lowest (3)MC state lies higher in energy than the lowest (3)MLCT one. This unprecedented energetic reversal in a series of iron complexes, with the stabilization of the charge-transfer state, opens up new perspectives towards iron-made excitonic and photonic devices, hampering the deactivation of the excitation via metal centered channels.

We hereby report studies devoted to a topological descriptor of photoinduced electronic charge density variation. Our novel index, symbolized as ϕS, consists in the detachment and attachment densities overlap, where the detachment density physically depicts the electron density removed from the ground state of a molecule during the transition while the attachment density consists in the rearranged density in the excited state. Our method provides a simple and efficient way to quantitatively evaluate how easy the charge-separation is made upon the chromophore's light absorption. Furthermore, this model can be applied for instance to address a comment on new push-pull dyes charge-transfer ability in order to assess their potentiality as candidates for light absorption-based devices. Moreover, the ϕS assessment allows us to perform some methodological diagnostic tests concerning the use of long-range corrected exchange-correlation functional in a time-dependent density functional theory (TDDFT) framework. This paper relates the ϕS descriptor's mathematical foundations from various perspectives (detachment/attachment densities or natural transition orbitals), together with its application to several types of chromophores. Connections and divergences with a formerly proposed index are finally evidenced.

In parallel with the derivation of a novel descriptor (ϕS) related to chromophores' electronic excited states topology, the present article emphasizes some congruence of significance between our ϕS index and formerly developed centroid-related indices. We especially point out the possibility to formally adapt a barycenter (centroid) approach to the use of detachment/attachment densities. While the reciprocity of the two approaches can be mathematically evidenced, we will show that some difficulties brought by the use of ground and excited states electron densities in direct space can be overcome by undertaking some operations on the Hilbert space-related detachment/attachment matrices. We further wish to point out the crucial case of some chromophores holding two electron-withdrawing groups symmetrically disposed in a rod-like structure. Finally, we will qualitatively highlight the quadratic-like relationship between the amount of displaced charge induced by light absorption and the ϕS index.

A Rashba/Dresselhaus band splitting has been recently measured in organohalide perovskites and invoked in various experiments as a possible cause for the reduced electron-hole recombination rates observed in this class of materials. In this Perspective, we discuss the interplay of electronic and nuclear degrees of freedom in defining such an effect in realistic methylammonium lead iodide (MAPbI) models. We distinguish between bulk and surface effects and find that, while a spatially local (in time and space) effect may be at work in the bulk, a "static" band-splitting effect is found at surfaces due to structural distortion. The proposed surface effect is consistent with the low surface recombination reported for MAPbI single crystals and might contribute to the success of organohalide perovskites.

New heteroleptic iron complexes mixing a terpyridine bearing a protonable pyridyl substituent (pytpy) and a pyridyl carbene ligand (carb) have been prepared and characterised by UV/Vis spectroscopy, cyclic voltammetry and TD-DFT computations. The absorption spectrum of [Fe(carb)-(pytpy)] 2+ showed a notable redshift compared with the homoleptic [Fe(carb) 2 ] 2+ complex. The MLCT transition oc-Boulevard des Aiguillettes, 54506 Vandoeuvre-Lès-Nancy, SynthesisLigand pytpy was chosen for the electron-accepting character of the pyridine ring and for the ability of the pyridine Scheme 2. Synthesis of carbene-containing complexes.

In this contribution, we report two different methodologies for characterizing the electronic structure reorganization occurring when a chromophore undergoes an electronic transition. For the first method, we start by setting the theoretical background necessary to the reinterpretation through simple tensor analysis of (i) the transition density matrix and (ii) the natural transition orbitals in the scope of reduced density matrix theory. This novel interpretation is made more clear thanks to a short compendium of the one-particle reduced density matrix theory in a Fock space. The formalism is further applied to two different classes of excited states calculation methods, both requiring a single-determinant reference, that express an excited state as a hole-particle mono-excited configurations expansion, to which particle-hole correlation is coupled (time-dependent Hartree-Fock/time-dependent density functional theory) or not (configuration interaction single/Tamm-Dancoff approximation). For the second methodology presented in this paper, we introduce a novel and complementary concept related to electronic transitions with the canonical transition density matrix and the canonical transition orbitals. Their expression actually reflects the electronic cloud polarisation in the orbital space with a decomposition based on the actual contribution of one-particle excitations from occupied canonical orbitals to virtual ones. This approach validates our novel interpretation of the transition density matrix elements in terms of the Euclidean norm of elementary transition vectors in a linear tensor space. A proper use of these new concepts leads to the conclusion that despite the different principles underlying their construction, they provide two equivalent excited states topological analyses. This connexion is evidenced through simple illustrations of (in)organic dyes electronic transitions analysis.