Gas Phase Hydrolysis and Oxo-Exchange of Actinide Dioxide Cations: Elucidating Intrinsic Chemistry from Protactinium to Einsteinium.

Gas-phase bimolecular reactions of metal cations with water provide insights into intrinsic characteristics of hydrolysis. For the actinide dioxide cations, actinyl(V) AnO2 + , melding of experiment and computation provides insights into trends for hydrolysis, as well as for oxo-exchange between actinyls and water that proceeds by a hydrolysis pathway. Here this line of inquiry is further extended into the actinide series with CCSD(T) computations of potential energy surfaces, for the reaction pathway for oxo-exchange through hydrolysis of nine actinyl(V) ions, from PaO2 + to EsO2 + . The computed surfaces are in accord with previous experimental results for oxo-exchange, and furthermore predict spontaneous exchange for CmO2 + , BkO2 + , CfO2 + and EsO2 + , but not for AmO2 + . Natural Bond Order analysis of the species involved in both hydrolysis and oxo-exchange reveals an inverse correlation between the barrier to hydrolysis and the charge on the actinide centre, q(An). Based on this correlation, it can be concluded that hydrolysis, and related phenomena such as oxo-exchange, become less favourable as the charge on the metal centre decreases. The new results provide a straightforward rationalization of trends across a wide swathe of the actinide series

Activation of Water by Pentavalent Actinide Dioxide Cations: Characteristic Curium Revealed by a Reactivity Turn after Americium.

Swapping of an oxygen atom of water with that of a pentavalent actinide dioxide cation, AnO2+ also called an "actinyl", requires activation of an An-O bond. It was previously found that such oxo exchange in the gas phase occurs for the first two actinyls, PaO2+ and UO2+, but not the next two, NpO2+ and PuO2+. The An-O bond dissociation energies (BDEs) decrease from PaO2+ to PuO2+, such that the observation of a parallel decrease in the An-O bond reactivity is intriguing. To elucidate oxo exchange, we here extend experimental studies to AmO2+, americyl(V), and CmO2+, curyl(V), which were produced in remarkable abundance by electrospray ionization of Am3+ and Cm3+ solutions. Like other AnO2+, americyl(V) and curyl(V) adsorb up to four H2O molecules to form tetrahydrates AnO2(H2O)4+ with the actinide hexacoordinated by oxygen atoms. It was found that AmO2+ does not oxo-exchange, whereas CmO2+ does, establishing a "turn" to increasing the reactivity from americyl to curyl, which validates computational predictions. Because oxo exchange occurs via conversion of an actinyl(V) hydrate, AnO2(H2O)+, to an actinide(V) hydroxide, AnO(OH)2+, it reflects the propensity for actinyl(V) hydrolysis: PaO2+ hydrolyzes and oxo-exchanges most easily, despite the fact that it has the highest BDE of all AnO2+. A reexamination of the computational results for actinyl(V) oxo exchange reveals distinctive properties and chemistry of curyl(V) species, particularly CmO(OH)2+

Remarkably High Stability of Late Actinide Dioxide Cations: Extending Chemistry to Pentavalent Berkelium and Californium.

Actinyl chemistry is extended beyond Cm to BkO2+ and CfO2+ through transfer of an O atom from NO2 to BkO+ or CfO+ , establishing a surprisingly high lower limit of 73 kcal mol-1 for the dissociation energies, D[O-(BkO+ )] and D[O-(CfO+ )]. CCSD(T) computations are in accord with the observed reactions, and characterize the newly observed dioxide ions as linear pentavalent actinyls; these being the first Bk and Cf species with oxidation states above IV. Computations of actinide dioxide cations AnO2+ for An=Pa to Lr reveal an unexpected minimum for D[O-(CmO+ )]. For CmO2+ , and AnO2+ beyond EsO2+ , the most stable structure has side-on bonded η2 -(O2 ), as AnIII peroxides for An=Cm and Lr, and as AnII superoxides for An=Fm, Md, and No. It is predicted that the most stable structure of EsO2+ is linear [O=EsV =O]+ , einsteinyl, and that FmO2+ and MdO2+ , like CmO2+ , also have actinyl(V) structures as local energy minima. The results expand actinide oxidation state chemistry, the realm of the distinctive actinyl moiety, and the non-periodic character towards the end of the periodic table

Theoretical and Experimental Study of the Excess Thermodynamic Properties of Highly Nonideal Liquid Mixtures of Butanol Isomers + DBE

Binary alcohol + ether liquid mixtures are of significant importance as potential biofuels or additives for internal combustion engines and attract considerable fundamental interest as model systems containing one strongly H-bonded self-associating component (alcohol) and one that is unable to do so (ether), but that can interact strongly as a H-bond acceptor. In this context, the excess thermodynamic properties of these mixtures, specifically the excess molar enthalpies and volumes (HE and VE), have been extensively measured. Butanol isomer + di-n-butyl ether (DBE) mixtures received significant attention because of interesting differences in their VE, changing from negative (1- and isobutanol) to positive (2- and tert-butanol) with increasing alkyl group branching. With the aim of shedding light on the differences in alcohol self-association and cross-species H-bonding, considered responsible for the observed differences, we studied representative 1- and 2-butanol + DBE mixtures by molecular dynamics simulations and experimental excess property measurements. The simulations reveal marked differences in the self-association of the two isomers and, while supporting the existing interpretations of the HE and VE in a general sense, our results suggest, for the first time, that subtle changes in H-bonded topologies may contribute significantly to the anomalous volumetric properties of these mixtures

Nanostructured PbS-doped inorganic film synthesized by sol-gel route

IV-VI semiconductor quantum dots embedded into an inorganic matrix represent nanostructured composite materials with potential application in temperature sensor systems. This study explores the optical, structural, and morphological properties of a novel PbS quantum dots (QDs)- doped inorganic thin film belonging to the Al2O3 -SiO2 -P2O5 system. The film was synthesized by the sol-gel method, spin coating technique, starting from a precursor solution deposited on a glass substrate in a multilayer process, followed by drying of each deposited layer. Crystalline PbS QDs embedded in the inorganic vitreous host matrix formed a nanocomposite material. Specific investigations such as X-ray diffraction (XRD), optical absorbance in the ultraviolet (UV)-visible (Vis)-near infrared (NIR) domain, NIR luminescence, Raman spectroscopy, scanning electron microscopy– energy dispersive X-ray (SEM-EDX), and atomic force microscopy (AFM) were used to obtain a comprehensive characterization of the deposited film. The dimensions of the PbS nanocrystallite phase were corroborated by XRD, SEM-EDX, and AFM results. The luminescence band from 1400 nm follows the luminescence peak of the precursor solution and that of the dopant solution. The emission of the PbS-doped film in the NIR domain is a premise for potential application in temperature sensing systems.This study was funded by a grant of the Romanian National Authority for Scientific Research and Innovation, CCCDI–UEFISCDI, project ERANET-MANUNET-TEMSENSOPT, MNET20/ NMCS3732, within PNCDI III, contract 213/02.12.2020; Ministry of Research, Innovation and Digitalization (MRID), Core Program, contracts no. 16N/2019, 18N/2019 and 21N/2019; MRID through Program I—Development of the National R & D System, Subprogram 1.2–Institutional Performance– Projects for Excellence Financing in RDI, contracts no. 13PFE/2021, 18PFE/2021 and 35PFE/2021; CCCDI-UEFISCDI project PN-III-P2-2.1-PED-2021-2541. Support from the Public University of Navarre for Research Groups is also acknowledged