POMSimulator: An open-source tool for predicting the aqueous speciation and self-assembly mechanisms of polyoxometalates.

Elucidating the speciation (in terms of concentration versus pH) and understanding the formation mechanisms of polyoxometalates remains a significant challenge, both in experimental and computational domains. POMSimulator is a new methodology that tackles this problem from a purely computational perspective. The methodology uses results from quantum mechanics based methods to automatically set up the chemical reaction network, and to build speciation models. As a result, it becomes possible to predict speciation and phase diagrams, as well as to derive new insights into the formation mechanisms of large molecular clusters. In this work we present the main features of the first open-source version of the software. Since the first report [Chem. Sci. 2020, 11, 8448-8456], POMSimulator has undergone several improvements to keep up with the growing challenges that were tackled. After four years of research, we recognize that the source code is sufficiently stable to share a polished and user-friendly version. The Python code, manual, examples, and install instructions can be found at https://github.com/petrusen/pomsimulator.

Computational Prediction of Speciation Diagrams and Nucleation Mechanisms: Molecular Vanadium, Niobium, and Tantalum Oxide Nanoclusters in Solution.

Understanding the aqueous speciation of molecular metal-oxo-clusters plays a key role in different fields such as catalysis, electrochemistry, nuclear waste recycling, and biochemistry. To describe the speciation accurately, it is essential to elucidate the underlying self-assembly processes. Herein, we apply a computational method to predict the speciation and formation mechanisms of polyoxovanadates, -niobates, and -tantalates. While polyoxovanadates have been widely studied, polyoxoniobates and -tantalates lack the same level of understanding. First, we propose a pentavanadate cluster ([V5O14]3-) as a key intermediate for the formation of the decavanadate. Our computed phase speciation diagram is in particularly good agreement with the experiments. Second, we report the formation constants of the heptaniobate, [Nb7O22]9-, decaniobate, [Nb10O28]6-, and tetracosaniobate [H9Nb24O72]15-. Additionally, we compute the speciation and phase diagram of niobium, which so far was restricted to Lindqvist derivates. Finally, we predict the formation constant of the decatantalate ([Ta10O26]6-) in water, even though it had only been synthesized in toluene. Furthermore, we also calculate the corresponding speciation and phase diagrams for polyoxotantalates. Overall, we show that our method can be successfully applied to different families of molecular metal oxides without any need for readjustments; therefore, it can be regarded as a trustworthy tool for exploring polyoxometalates' chemistry.

Mechanistic insights of molecular metal polyselenides for catalytic hydrogen generation.

Molecular metal chalcogenides have attracted great attention as electrocatalysts for the hydrogen evolution reaction (HER). However, efficient utilisation of the active sites and catalytic performance modulation has been challenging. Here we explore the design of immobilized molecular molybdenum polyselenides [Mo2O2S2(Se2)(Sex)]2- that exhibit efficient hydrogen evolution at low overpotential and stability over 1000 cycles. Density functional calculations provide evidence of a unimolecular mechanism in the HER process via the exploration of viable reaction pathways. The discussed findings are of a broad interest in the development of efficient molecular electrocatalytic materials.

Radical recombination in interstellar ices, a not so simple mechanism.

Many complex organic molecules (hereafter COMs) have been detected in different regions of the interstellar medium (ISM). In each region, different energetic processes - UV irradiation, atom bombardments, etc. - that could be linked to the formation of detected COMs may occur depending on the environment. Several formation mechanisms were proposed but increasing attention is paid to radical recombination reactions. Previous studies showed that glycolaldehyde (HC(O)CH2OH) and ethylene glycol (HOCH2CH2OH) are formed by radical recombination between HC˙O and ˙CH2OH, and by ˙CH2OH dimerisation, respectively. Formyl (HC˙O), one of the most famous astrophysically-relevant radical species, has been detected as a gaseous component of the ISM. Its reactivity was already attributed to the formation of several COMs. This work aims to study the dimerisation of formyl radical HC˙O using a cryogenic matrix technique. The evolution of the chemical sample composition is monitored by infrared spectroscopy and by mass spectrometry during temperature programmed desorption (TPD) monitoring. Results indicate that the reaction of one HC˙O with another does not lead to the direct formation of glyoxal (HC(O)C(O)H) but yields H2CO and CO. Results are also compared with those for the reaction between two ˙CH2OH radicals and the recombination between HC˙O and ˙CH2OH. Also, glyceraldehyde was tentatively detected in our experiment using different spectroscopic techniques. A radical mechanism is proposed to explain its formation in our experiments. Complementary quantum chemical calculations provide an atomistic interpretation of the experimental findings.

Excitation Dynamics in Hetero-bichromophoric Calixarene Systems.

In this work, the dynamics of electronic energy transfer (EET) in bichromophoric donor-acceptor systems, obtained by functionalizing a calix[4]arene scaffold with two dyes, was experimentally and theoretically characterized. The investigated compounds are highly versatile, due to the possibility of linking the dye molecules to the cone or partial cone structure of the calix[4]arene, which directs the two active units to the same or opposite side of the scaffold, respectively. The dynamics and efficiency of the EET process between the donor and acceptor units was investigated and discussed through a combined experimental and theoretical approach, involving ultrafast pump-probe spectroscopy and density functional theory based characterization of the energetic and spectroscopic properties of the system. Our results suggest that the external medium strongly determines the particular conformation adopted by the bichromophores, with a direct effect on the extent of excitonic coupling between the dyes and hence on the dynamics of the EET process itself.

Combination of transient 2D-IR experiments and ab initio computations sheds light on the formation of the charge-transfer state in photoexcited carbonyl carotenoids.

The excited state dynamics of carbonyl carotenoids is very complex because of the coupling of single- and doubly excited states and the possible involvement of intramolecular charge-transfer (ICT) states. In this contribution we employ ultrafast infrared spectroscopy and theoretical computations to investigate the relaxation dynamics of trans-8'-apo-ß-carotenal occurring on the picosecond time scale, after excitation in the S2 state. In a (slightly) polar solvent like chloroform, one-dimensional (T1D-IR) and two-dimensional (T2D-IR) transient infrared spectroscopy reveal spectral components with characteristic frequencies and lifetimes that are not observed in nonpolar solvents (cyclohexane). Combining experimental evidence with an analysis of CASPT2//CASSCF ground and excited state minima and energy profiles, complemented with TDDFT calculations in gas phase and in solvent, we propose a photochemical decay mechanism for this system where only the bright single-excited 1Bu(+) and the dark double-excited 2Ag(-) states are involved. Specifically, the initially populated 1Bu(+) relaxes toward 2Ag(-) in 200 fs. In a nonpolar solvent 2Ag(-) decays to the ground state (GS) in 25 ps. In polar solvents, distortions along twisting modes of the chain promote a repopulation of the 1Bu(+) state which then quickly relaxes to the GS (18 ps in chloroform). The 1Bu(+) state has a high electric dipole and is the main contributor to the charge-transfer state involved in the dynamics in polar solvents. The 2Ag(-) → 1Bu(+) population transfer is evidenced by a cross peak on the T2D-IR map revealing that the motions along the same stretching of the conjugated chain on the 2Ag(-) and 1Bu(+) states are coupled.