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Register a new userImproved Charge Transfer Multiplet Method to Simulate M- and L-Edge X-ray Absorption Spectra of Metal-Centered Excited States
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Charge transfer multiplet (CTM) theory is a computationally undemanding and highly mature method for simulating the soft X-ray spectra of first-row transition metal complexes. However, CTM theory has seldom been applied to the simulation of excited state spectra. In this article, we extend the CTM4XAS software package to simulate M2,3- and L2,3-edge spectra of excited states of first-row transition metals and to interpret CTM eigenfunctions in terms of Russell-Saunders term symbols. We use these new programs to reinterpret the recently reported excited state M2,3-edge difference spectra of photogenerated ferrocenium cations and propose alternative assignments for the electronic state of the photogenerated ferrocenium cations supported by CTM theory simulations. We also use these new programs to model the L2,3-edge spectra of FeII compounds during nuclear relaxation following photoinduced spin crossover, and propose spectroscopic signatures for their vibrationally hot states
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Fast and inexpensive characterization of materials properties is a key element to discover novel functional materials. In this work, we suggest an approach employing three classes of Bayesian machine learning (ML) models to correlate electronic absorption spectra of nanoaggregates with the strength of intermolecular electronic couplings in organic conducting and semiconducting materials. As a specific model system, we consider PEDOT:PSS, a cornerstone material for organic electronic applications, and so analyze the couplings between charged dimers of closely packed PEDOT oligomers that are at the heart of the materials unrivaled conductivity. We demonstrate that ML algorithms can identify correlations between the coupling strengths and the electronic absorption spectra. We also show that ML models can be trained to be transferable across a broad range of spectral resolutions, and that the electronic couplings can be predicted from the simulated spectra with an 88 % accuracy when ML models are used as classifiers. Although the ML models employed in this study were trained on data generated by a multi-scale computational workflow, they were able to leverage leverage experimental data.
This Perspective describes current computational efforts in the field of simulating photodynamics of transition metal complexes. We present the typical workflows and feature the strengths and limitations of the different contemporary approaches. From electronic structure methods suitable to describe transition metal complexes to approaches able to simulate their nuclear dynamics under the effect of light, we lay particular attention to build a bridge between theory and experiment by critically discussing the different models commonly adopted in the interpretation of spectroscopic experiments and the simulation of particular observables. Thereby, we review all the studies of excited state dynamics on transition metal complexes, both in gas phase and in solution from reduced to full dimensionality
Time-resolved spectroscopy provides the main tool for analyzing the dynamics of excitonic energy transfer in light-harvesting complexes. To infer time-scales and effective coupling parameters from experimental data requires to develop numerical exact theoretical models. The finite duration of the laser-molecule interactions and the reorganization process during the exciton migration affect the location and strength of spectroscopic signals. We show that the non-perturbative hierarchical equations of motion (HEOM) method captures these processes in a model exciton system, including the charge transfer state.
The authors present a technique using variational Monte Carlo to solve for excited states of electronic systems. The technique is based on enforcing orthogonality to lower energy states, which results in a simple variational principle for the excited states. Energy optimization is then used to solve for the excited states. An application to the well-characterized benzene molecule, in which ~10,000 parameters are optimized for the first 12 excited states.Agreement within approximately 0.15 eV is obtained with higher scaling coupled cluster methods; small disagreements with experiment are likely due to vibrational effects.
Luminescence spectra of NiO have been investigated under vacuum ultraviolet (VUV) and soft X-ray (XUV) excitation. Photoluminescence (PL) spectra show broad emission bands centered at about 2.3 and 3.2 eV. The PL excitation (PLE) spectral evolution and lifetime measurements reveal that two mechanisms with short and long decay times, attributed to the d($e_g$)-d($e_g$) and p($pi$)-d charge transfer (CT) transitions in the range 4-6,eV, respectively, are responsible for the observed emissions, while the most intensive p($sigma$)-d CT transition at 7,eV appears to be a weak if any PL excitation mechanism. The PLE spectra recorded in the 4-7,eV range agree with the RIXS and reflectance data. Making use of the XUV excitation allows us to avoid the predominant role of the surface effects in luminescence and reveal bulk luminescence with puzzling well isolated doublet of very narrow lines with close energies near 3.3,eV characteristic for recombination transitions in self-trapped emph{d}-emph{d} CT excitons formed by coupled Jahn-Teller Ni$^+$ and Ni$^{3+}$ centers. This conclusion is supported both by a comparative analysis of the luminescence spectra for NiO and solid solutions Ni$_{x}$Zn$_{1-x}$O, and by a comprehensive cluster model assignement of different emph{p}-emph{d} and emph{d}-emph{d} CT transitions, their relaxation channels. To the best of our knowledge it is the first observation of the self-trapping for emph{d}-emph{d} CT excitons. Our paper shows the time resolved luminescence measurements provide an instructive tool for elucidation of the emph{p}-emph{d} and emph{d}-emph{d} CT excitations and their relaxation in 3d oxides.
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