Observing the Role of Electron Delocalization in Electronic Transport by Incorporating Actinides into Ligated Metal-Chalcogenide Superatoms.

Since delocalization of electronic states is a prerequisite for exerting unique electron transport properties, early actinides (An) with highly delocalized 5f/6d orbitals are natural candidates. However, given the experimental difficulties of such radioactive compounds and the complex relativistic effects in theoretical studies, understanding the electronic structure and bonding of actinides is underdeveloped on the periodic table. A further challenge is the very complicated electronic structures encountered in the confinement of actinides, as vividly illustrated by the weakly radioactive Th(Thorium)-encapsulated metal chalcogenide clusters, Th@Co6Te8L6 (L = PH3, PMe3, PEt3). Here we report the electronic structure and the electron transport properties of the Th@Co6Te8L6 clusters and compare them with those of the hollow Co6Te8L6 clusters using the nonequilibrium Green's function combined with relativistic density functional theory (NEGF-DFT). We found that the equilibrium conductance in Th@Co6Te8(PH3)6 (0.76 G0) has been greatly improved over that in Co6Te8(PH3)6 (0.03 G0), which has also been verified under an applied different bias voltage. The covalent bonding character between 6d (Th) and 3d (Co) atomic orbitals resulting from steric confinement is the source of the performance enhancement and a most important factor governing the accessibility of such 5f/6d orbitals. The results are of significance to the rapidly developing field of molecular nanoelectronics.

Bis(acyl)phosphide Complexes of U(III)/U(IV): A Case of a Hidden Redox-Active Ligand.

The recently reported tris(bis(2,4,6-triisopropylbenzoyl)-phosphide)uranium (UIII(trippBAP)3, 2) complex (Inorg. Chem. 2022, 61 (32), 12508-12517) demonstrated a silent 31P NMR spectrum. This complex was described as a U(III) complex with an organic radical ligand fragment. Moreover, the EPR spectrum of 2 was indicative of an organic radical in the ligand framework complexed to uranium, in contrast to that of UIV(mesBAP)4, 1. Herein, with the help of relativistic density functional theory (DFT) calculations, the electronic structures of 1, 2, and U(mesBAP)3 (4) are examined in an effort to understand the unusual 31P NMR spectrum of 2. Results indicate the reduction of the carbonyl bonds and delocalization of the electrons over the ligands, indicative of U → L backbonding. Additionally, the reduced acyl carbons are found to exist as ketyl radicals [O═C• -] that are responsible for the silent 31P NMR spectra of 2. These findings demonstrate the redox noninnocent nature of BAP- in 2 and 4, causing uranium to exist in a formal oxidation state of +4.

The effect of ancillary ligands on hydrocarbon C-H bond functionalization by uranyl photocatalysts.

The aqueous uranyl dication has long been known to facilitate the UV light-induced decomposition of aqueous VOCs (volatile organic compounds), via the long-lived highly efficient, uranyl excited state. The lower-energy visible light excited uranyl ion is also able to cleave unactivated hydrocarbon C-H bonds, yet the development of this reactivity into controlled and catalytic C-H bond functionalization is still in its infancy, with almost all studies still focused on uranyl nitrate as the precatalyst. Here, hydrocarbon-soluble uranyl nitrate and chloride complexes supported by substituted phenanthroline (Ph2phen) ligands are compared to each other, and to the parent salts, as photocatalysts for the functionalization of cyclooctane by H atom abstraction. Analysis of the absorption and emission spectra, and emission lifetimes of Ph2phen-coordinated uranyl complexes demonstrate the utility of the ligand in light absorption in the photocatalysis, which is related to the energy and kinetic decay profile of the uranyl photoexcited state. Density functional theory computational analysis of the C-H activation steps in the reaction show how a set of dispersion forces between the hydrocarbon substrate and the Ph2phen ligand provide control over the H atom abstraction, and provide predictions of selectivity of H atom abstraction by the uranyl oxo of the ring C-H over the ethyl C-H in an ethylcyclohexane substrate.

Computational study of core modified dipyriamethyrin for the competitive complexation of Am3+/Cm3+ from their trichlorides.

In the process of handling and storage of radioactive actinides it is essential to selectively sequester the minor actinides, such as Am and Cm, through a competitive complexation process. Herein we computationally designed two core modified ligands (L21- and L3) through systematic oxygen substitution at the NH sites of dipyriamethyrin (L1_2H), a hexadentate expanded porphyrin, and studied their competitive complexation towards trivalent actinides (An = Am/Cm) from their trichlorides using density functional theory (DFT). We observed shorter An-N bonds and longer An-O bonds in complexes based on core modified ligands (L21- and L3). The An-Cl bond length increases with increasing axial coordination number (i.e., from L12- to L3) to accommodate the ligands. All the bonds were identified to be electrostatic in nature. L12- exhibits shorter bonds and larger bond orders on complexing with Am than with Cm. On moving from complexes of L21- to L3, the An-N bond lengths are shortened, while An-O bond lengths become larger. Between the complexes of Am and Cm, there is marginal difference in their bond distances with L21- and L3. Charge analysis shows ligand to metal charge transfer during coordination, with back-donation from An to N/O and Cl. The calculated spin-density analysis indicates that An remains in its trivalent oxidation state on complexation, while orbital occupation analysis shows that the 5f and 6d orbitals are involved in bonding; this was confirmed by molecular orbital (MO) analysis that shows the complexes of L21- and L3 to exhibit higher degeneracy in their overlapping MOs. Further, the energy decomposition analysis (EDA) confirms that all ionic bonds are primarily due to electrostatic contributions, where the orbital contributions increase from L12- to L3 complexes and maximum covalency was observed in Cm complexes due to the energy matching between the 5f orbitals of Cm and the 2p orbitals of N and Cl, compared to Am. To confirm the competitiveness in the complexation of the ligand towards Am vs. Cm, the thermodynamic parameters were analysed for the ligand and metal substitution reactions. L12- shows more affinity towards Am than Cm, while L21- and L3 prefer Cm.

Interactions between Metals and Eudistomins of Ascidian Origin: A Computational Study.

Ascidians are marine animals that adopt unusual techniques to deter predation. The three main methods are sequestration of unusual metals, high concentrations of sulfuric acid/sulfate ions in tunicate cells, and the presence of eudistomins. In this study, we hypothesize that ascidians sequester metals in their sulfate form, and the complexation of eudistomins with the metals could liberate the sulfate ion. Three representative metal aqua ions were chosen, viz., vanadyl, uranyl, and thorium ions, as well as four simple eudistomins which act as bidentate ligands, viz., eudistomin-W, debromoeudistomin-K, eudistomidin-C, and eudistomidin-B. By designing 7 model reactions, we tested our hypothesis using density functional theory (DFT) methods PBE-D3, BLYP, and B3LYP. The ΔG values of the model reactions provide strong support for our hypothesis. To verify the hypothesis further, we calculated the metal-eudistomin interactions with Be, Zn, and Pb. Based on our results, we suggest that ascidians may not prefer any particular metal. In addition, despite using different DFT functionals, we have observed similar ΔG values for each case. With our work, we have successfully used computational tools in our attempt to understand the unique behavior of ascidians.

Periodic trends in trivalent actinide halides, phosphates, and arsenates.

Due to the limited abundance of the actinide elements, computational methods, for now, remain an exclusive avenue to investigate the periodic trends across the actinide series. As every actinide element can exhibit a +3-oxidation state, we have explored model systems of gas-phase actinide trihalides, phosphates, and arsenates across the series to capture the periodic trends. By doing so, we were able to capture the periodic trends down the halogen series as well, and for the first time we are reporting a study on actinide astatides. Using scalar and spin-orbit relativistic Density Functional Theory (DFT) calculations, we have explored the variations in bond lengths, bond angles, and the charges on actinides (An). Despite the use of different sets of ligands, the trends remain similar. The properties of trivalent Pa, U, Np, and Pu are nearly identical; similar ionic radii could be the reason. The actinide elements show a tendency to exhibit a pre-Pu and a post-Cm behaviour, with Am acting as a switch. This could be due to the change in the behaviour from d-f-type to f-filling/d-type at around Pu-Cm in the actinides as already proposed in the previous literature. Bond lengths in the AnX3 increase down the halide series, and the atomic charges decrease on the actinide elements.

Precise Recognition in Water by an Endo-Functionalized Cavity: Tuning the Complementarity of Binding Sites.

Precise binding towards structurally similar substrates is a common feature of biomolecular recognition. However, achieving such selectivity-especially in distinguishing subtle differences in substrates-with synthetic hosts can be quite challenging. Herein, we report a novel design strategy involving the combination of different rigid skeletons to adjust the distance between recognition sites within the cavity, which allows for the highly selective recognition of hydrogen-bonding complementary substrates, such as 4-chromanone. X-ray single-crystal structures and density functional theory calculations confirmed that the distance of endo-functionalized groups within the rigid cavity is crucial for achieving high binding selectivity through hydrogen bonding. The thermodynamic data and molecular dynamics simulations revealed a significant influence of the hydrophobic cavity on the binding affinity. The new receptor possesses both high selectivity and high affinity, which provide valuable insights for the design of customized receptors.

Periodic Trends in the Stabilization of Actinyls in Their Higher Oxidation States Using Pyrrophen Ligands.

Owing to the prominent existence and unique chemistry of actinyls, their complexation with suitable ligands is of significant interest. The complexation of high-valent actinyl moieties (An = U, Np, Pu and Am) with the acyclic sal-porphyrin analogue called "pyrrophen" (L(1)) and its dimethyl derivative (L(2)) with four nitrogen and two oxygen donor atoms was studied using relativistic density functional theory. Based on the periodic trends, the [UVO2-L(1)/L(2)]1- complexes show shorter bond lengths and higher bond orders that increase across the series of pentavalent actinyl complexes mainly due to the localization of the 5f orbitals. Among the hexavalent complexes, the [UVIO2-L(1)/L(2)] complexes have the shortest bonds. Following the uranyl complex, due to the plutonium turn, the [AmVIO2-L(1)/L(2)] complexes exhibit comparable properties with those of the former. Charge analysis suggests the complexation to be facilitated through ligand-to-metal charge transfer (LMCT) mainly through σ donation. Thermodynamic feasibility of complexation was modeled using hydrated actinyl moieties in aqueous medium and was found to be spontaneous. The dimethylated pyrrophen (L(2)) shows higher magnitudes of thermodynamic parameters indicating increased feasibility compared to the unsubstituted ligand (L(1)). Energy decomposition analysis (EDA) along with extended transition-state-natural orbitals for chemical valence theory (ETS-NOCV) analysis shows that the dominant electrostatic contributions decrease across the series and are counteracted by Pauli repulsion. Slight but considerable covalency is provided to hexavalent actinyl complexes by orbital contributions; this was confirmed by molecular orbital (MO) analysis that suggests strong covalency in americyl (VI) complexes. In addition to the pentavalent and hexavalent actinyl moieties, heptavalent actinyl species of neptunyl, plutonyl, and americyl were studied. Beyond the influence of the charges, the geometric and electronic properties point to the stabilization of neptunyl (VII) in the pyrrophen ligand environment, while the others shift to a lower (+VI) and relatively stable OS on complexation.

Understanding the Coordination Chemistry of AmIII/CmIII in the DOTA Cavity: Insights from Energetics and Electronic Structure Theory.

The minor actinides Am/Cm show multiple possibilities for coordination, providing great opportunities for their extraction and adsorption separation. Herein, we report complexation in an aqueous medium of AmIII/CmIII in the DOTA (H4DOTA = 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid) cavity with axial ligands (OH-, F-, and H2O), based on the energetics and electronic structure properties using density functional theory (DFT). The formation and substitution reactions of OH--capped complexes are more likely to occur due to their enhanced hydration Gibbs free energies, followed by F-, and then H2O. Both the longer An-ODOTA bond lengths and the larger bite angle (∠O-An-O) in the OH--capped complexes reflect the enhanced coordination provided by the axial ligand, slightly less so for F-. Energy decomposition analysis based on the electronic structure supports the preference for OH--capped complexes with a near-perfect balance between attractive and repulsive contributions toward the interaction. Furthermore, molecular orbital analysis revealed that the frontier molecular orbitals of Am and Cm complexes are substantially different; that is, the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) compositions of the Am complexes are all contributed by 5f, while the HOMO and LUMO compositions of the Cm complexes are derived from 5f and 6d, respectively. Finally, the metal-exchange reactions demonstrate competitive complexation of DOTA toward AmIII over CmIII for the OH--capped system. These results imply the importance of coordination chemistry in actinide chemistry in general and specifically in AmIII/CmIII solution chemistry.

Comparative Study of a Decadentate Acyclic Chelate, HOPO-O10, and Its Octadentate Analogue, HOPO-O8, for Radiopharmaceutical Applications.

Radiolanthanides and actinides are aptly suited for the diagnosis and treatment of cancer via nuclear medicine because they possess unique chemical and physical properties (e.g., radioactive decay emissions). These rare radiometals have recently shown the potential to selectively deliver a radiation payload to cancer cells. However, their clinical success is highly dependent on finding a suitable ligand for stable chelation and conjugation to a disease-targeting vector. Currently, the commercially available chelates exploited in the radiopharmaceutical design do not fulfill all of the requirements for nuclear medicine applications, and there is a need to further explore their chemistry to rationally design highly specific chelates. Herein, we describe the rational design and chemical development of a novel decadentate acyclic chelate containing five 1,2-hydroxypyridinones, 3,4,3,3-(LI-1,2-HOPO), referred to herein as HOPO-O10, based on the well-known octadentate ligand 3,4,3-(LI-1,2-HOPO), referred to herein as HOPO-O8, a highly efficient chelator for 89Zr[Zr4+]. Analysis by 1H NMR spectroscopy and mass spectrometry of the La3+ and Tb3+ complexes revealed that HOPO-O10 forms bimetallic complexes compared to HOPO-O8, which only forms monometallic species. The radiolabeling properties of both chelates were screened with [135La]La3+, [155/161Tb]Tb3+, [225Ac]Ac3+ and, [227Th]Th4+. Comparable high specific activity was observed for the [155/161Tb]Tb3+ complexes, outperforming the gold-standard 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid, yet HOPO-O10 surpassed HOPO-O8 with higher [227Th]Th4+ affinity and improved complex stability in a human serum challenge assay. A comprehensive analysis of the decadentate and octadentate chelates was performed with density functional theory for the La3+, Ac3+, Eu3+, Tb3+, Lu3+, and Th4+ complexes. The computational simulations demonstrated the enhanced stability of Th4+-HOPO-O10 over Th4+-HOPO-O8. This investigation reveals the potential of HOPO-O10 for the stable chelation of large tetravalent radioactinides for nuclear medicine applications and provides insight for further chelate development.

Selective Chelation of the Exotic Meitner-Auger Emitter Mercury-197 m/g with Sulfur-Rich Macrocyclic Ligands: Towards the Future of Theranostic Radiopharmaceuticals.

Mercury-197 m/g are a promising pair of radioactive isomers for incorporation into a theranostic as they can be used as a diagnostic agent using SPECT imaging and a therapeutic via Meitner-Auger electron emissions. However, the current absence of ligands able to stably coordinate 197m/g Hg to a tumour-targeting vector precludes their use in vivo. To address this, we report herein a series of sulfur-rich chelators capable of incorporating 197m/g Hg into a radiopharmaceutical. 1,4,7,10-Tetrathia-13-azacyclopentadecane (NS4 ) and its derivatives, (2-(1,4,7,10-tetrathia-13-azacyclopentadecan-13-yl)acetic acid (NS4 -CA) and N-benzyl-2-(1,4,7,10-tetrathia-13-azacyclopentadecan-13-yl)acetamide (NS4 -BA), were designed, synthesized and analyzed for their ability to coordinate Hg2+ through a combination of theoretical (DFT) and experimental coordination chemistry studies (NMR and mass spectrometry) as well as 197m/g Hg radiolabeling studies and in vitro stability assays. The development of stable ligands for 197m/g Hg reported herein is extremely impactful as it would enable their use for in vivo imaging and therapy, leading to personalized treatments for cancer.

Actinium coordination chemistry: A density functional theory study with monodentate and bidentate ligands.

In the current study, the coordination chemistry of nine-coordinate Ac(III) complexes with 35 monodentate and bidentate ligands was investigated using density functional theory (DFT) in terms of their geometries, charges, reaction energies, and bonding interactions. The energy decomposition analysis with naturals orbitals for chemical valence (EDA-NOCV) and the quantum theory of atoms in molecules (QTAIM) were employed as analysis methods. Trivalent Ac exhibits the highest affinities toward hard acids (such as charged oxophilic donors, fluoride), so its classification as a hard acid is justified. Natural population analysis quantified the involvement of 5f orbitals on Ac to be about 30% of total valence electron natural configuration indicating that Ac is a member of the actinide series. Pearson correlation coefficients were used to study the pairwise correlations among the bond lengths, ΔG reaction energies, charges on Ac and donor atoms, and data from EDA-NOCV and QTAIM. Strong correlations and anticorrelations were found between Voronoi charges on donor atoms with ΔG, EDA-NOCV interaction energies and QTAIM bond critical point densities.

Uranium(iv) alkyl cations: synthesis, structures, comparison with thorium(iv) analogues, and the influence of arene-coordination on thermal stability and ethylene polymerization activity.

Reaction of [(XA2)U(CH2SiMe3)2] (1; XA2 = 4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene) with 1 equivalent of [Ph3C][B(C6F5)4] in arene solvents afforded the arene-coordinated uranium alkyl cations, [(XA2)U(CH2SiMe3)(η n -arene)][B(C6F5)4] {arene = benzene (2), toluene (3), bromobenzene (4) and fluorobenzene (5)}. Compounds 2, 3, and 5 were crystallographically characterized, and in all cases the arene is π-coordinated. Solution NMR studies of 2-5 suggest that the binding preferences of the [(XA2)U(CH2SiMe3)]+ cation follow the order: toluene ≈ benzene > bromobenzene > fluorobenzene. Compounds 2-4 generated in C6H5R (R = H, Me or Br, respectively) showed no polymerization activity under 1 atm of ethylene. By contrast, 5 and 5-Th (the thorium analogue of 5) in fluorobenzene at 20 and 70 °C achieved ethylene polymerization activities between 16 800 and 139 200 g mol-1 h-1 atm-1, highlighting the extent to which common arene solvents such as toluene can suppress ethylene polymerization activity in sterically open f-element complexes. However, activation of [(XA2)An(CH2SiMe3)2] {M = U (1) or Th (1-Th)} with [Ph3C][B(C6F5)4] in n-alkane solvents did not afford an active polymerization catalyst due to catalyst decomposition, illustrating the critical role of PhX (X = H, Me, Br or F) coordination for alkyl cation stabilization. Gas phase DFT calculations, including fragment interaction calculations with energy decomposition and ETS-NOCV analysis, were carried out on the cationic portion of 2'-Th, 2', 3' and 5' (analogues of 2-Th, 2, 3 and 5 with hydrogen atoms in place of ligand backbone methyl and tert-butyl groups), providing insight into the nature of actinide-arene bonding, which decreases in strength in the order 2'-Th > 2' ≈ 3' > 5'.

Advancing the Am Extractant Design through the Interplay among Planarity, Preorganization, and Substitution Effects.

Advancing the field of chemical separations is important for nearly every area of science and technology. Some of the most challenging separations are associated with the americium ion Am(III) for its extraction in the nuclear fuel cycle, 241Am production for industrial usage, and environmental cleanup efforts. Herein, we study a series of extractants, using first-principle calculations, to identify the electronic properties that preferentially influence Am(III) binding in separations. As the most used extractant family and because it affords a high degree of functionalization, the polypyridyl family of extractants is chosen to study the effects of the planarity of the structure, preorganization of coordinating atoms, and substitution of various functional groups. The actinyl ions are used as a structurally simplified surrogate model to quickly screen the most promising candidates that can separate these metal ions. The down-selected extractants are then tested for the Am(III)/Eu(III) system. Our results show that π interactions, especially those between the central terpyridine ring and Am(III), play a crucial role in separation. Adding an electron-donating group onto the terpyridine backbone increases the binding energies to Am(III) and stabilizes Am-terpyridine coordination. Increasing the planarity of the extractant increases the binding strength as well, although this effect is found to be rather weak. Preorganizing the coordinating atoms of an extractant to their binding configuration as in the bound metal complex speeds up the binding process and significantly improves the kinetics of the separation process. This conclusion is validated by the synthesized 1,2-dihydrodipyrido[4,3-b;5,6-b]acridine (13) extractant, a preorganized derivative of the terpyridine extractant, which we experimentally showed was four times more effective than terpyridine at separating Am3+ from Eu3+ (SFAm/Eu ∼ 23 ± 1).

Chemical bonding in actinyl(V/VI) dipyriamethyrin complexes for the actinide series from americium to californium: a computational investigation.

The separation of minor actinides in their dioxocation (i.e., actinyl) form in high-valence oxidation states requires efficient ligands for their complexation. In this work, we evaluate the complexation properties of actinyls including americyl, curyl, berkelyl, and californyl in their pentavalent and hexavalent oxidation states with the dipyriamethyrin ligand (L) using density functional theory calculations. The calculated bond parameters show shorter AnOyl bonds with covalent character and longer An-N bonds with ionic character. The bonding between the actinyl cation and the ligand anion shows a flow of charges from the ligand to actinyl in all [AnV/VIO2-L]1-/0 complexes. However, across the series, backdonation of charges from the metal to the ligand becomes prominent and stabilizes the complexes. The thermodynamic parameters in the gas phase and solution suggest that the complex formation reaction is spontaneous for [CfV/VIO2-L]1-/0 complexes and spontaneous at elevated temperatures (>298.15 K) for all other complexes. Spin-orbit corrections have a quantitative impact while the overall trend remains the same. Energy decomposition analysis (EDA) reveals that the interaction between actinyl and the ligand is mainly due to electrostatic contributions that decrease from Am to Cf along with an increase in orbital contributions due to the backdonation of charges from the actinyl metal center to the ligand that greatly stabilizes the Cf complex. The repulsive Pauli energy contribution is observed to increase in the case of [AnVO2-L]1- complexes from Am to Cf while a decrease is observed among [AnVIO2-L]0 complexes, showing minimum repulsion in [CfVIO2-L]0 complex formation. Overall, the hexavalent actinyl complexes show greater stability (increasing from Am to Cf) than their pentavalent counterparts.

Achieved negative differential resistance behavior of Si/B-substituted into a C6 chain sandwiched between capped carbon nanotube junctions.

Electronic transport properties of a pristine C6 chain and Si/B-substituted into the C6 chain sandwiched between two (5, 5) capped carbon nanotube electrodes were investigated through first-principles calculations based on non-equilibrium Green's functions (NEGF) conjugated with density functional theory (DFT). Si and B substitutions will affect the I-V curve of a pristine C6 chain. In the I-V characteristics, multi negative differential resistance (NDR) with large peak to valley ratio (PVR) and rectifying actions were observed. The NDR behavior originates from the joining and moving of conduction orbitals inside and outside of the bias window at a certain bias voltage. Furthermore, the assessment of transmission coefficient and distribution of molecular orbitals reveals that the rectifying performance is the result of the asymmetric distribution of the frontier molecular orbitals in the central region and their coupling with the electrodes. Multi NDR behavior of B substitution under very low bias voltage is a unique property of our proposed devices. Moreover, the CNT|C-(B-C)2-C|CNT molecular device shows a high PVR up to 31.8, which demonstrates that the proposed devices can be useful for molecular switching in nanoelectronic devices.

Methods for Interpreting the Partitioning and Fate of Petroleum Hydrocarbons in a Sea Ice Environment.

Decreases in Arctic Sea ice extent and thickness have led to more open ice conditions, encouraging both shipping traffic and oil exploration within the northern Arctic. As a result, the increased potential for accidental releases of crude oil or fuel into the Arctic environment threatens the pristine marine environment, its ecosystem, and local inhabitants. Thus, there is a need to develop a better understanding of oil behavior in a sea ice environment on a microscopic level. Computational quantum chemistry was used to simulate the effects of evaporation, dissolution, and partitioning within sea ice. Vapor pressures, solubilities, octanol-water partition coefficients, and molecular volumes were calculated using quantum chemistry and thermodynamics for pure liquid solutes (oil constituents) of interest. These calculations incorporated experimentally measured temperatures and salinities taken throughout an oil-in-ice mesocosm experiment conducted at the University of Manitoba in 2017. Their potential for interpreting the relative movements of oil constituents was assessed. Our results suggest that the relative movement of oil constituents is influenced by differences in physical properties. Lighter molecules showed a greater tendency to be controlled by brine advection processes due to their greater solubility. Molecules which are more hydrophobic were found to concentrate in areas of lower salt concentration.

Prediction of beryllium clusters (Ben; n = 3-25) from first principles.

Evolutionary searches using the USPEX method (Universal Structure Predictor: Evolutionary Xtallography) combined with density functional theory (DFT) calculations were performed to obtain the global minimum structures of beryllium (Ben, n = 3-25) clusters. The thermodynamic stability, optoelectronic and photocatalytic properties as well as the nature of bonding are considered for the most stable clusters. It is found that the cluster with n = 15 is the transition point at which the configurations change from 3D hollow cages to filled cage structures (with an interior atom appearing in the structure). All the ground state structures are energetically favorable with negative binding energies, suggesting good synthetic feasibility for these structures. The calculated relative stabilities and electronic structure show that the Be4, Be10 and, Be17 clusters are the most stable structures and can be considered as superatoms. The electron configurations of Be4, Be10 and Be17 clusters with 8, 20 and 34 electrons are identified as 1S2 1P6, 1S2 1P6 1D10 2S2, 1S2 1P6 1D10 2S2 1F14, respectively. Theoretical simulations determined that all the ground state structures exhibit excellent thermal stability, where the upper-limit temperature that the structures can tolerate is 900 K. During AIMD simulation of O2 adsorption onto the Be17 cluster an interesting phenomenon was happening in which the pristine Be17 cluster becomes a new stable Be17O16 cluster. Based on ELF (electron localization function) analysis, it can be concluded that the Be-Be bonds in the small clusters are primarily of van der Waals type, while for the larger clusters, the bonds are of metallic nature. The Ben clusters show very strong absorption in the UV and visible regions with absorption coefficients larger than 105 cm-1, which suggests a wide range of potential advanced optoelectronics applications. The Be17 cluster has a suitable band alignment in the visible-light excitation region which will produce enhanced photocatalytic activities (making it a promising material for water splitting).

Stabilization of hydrated AcIII cation: the role of superatom states in actinium-water bonding.

225Ac-based radiopharmaceuticals have the potential to become invaluable in designated cancer therapy. However, the limited understanding of the solution chemistry and bonding properties of actinium has hindered the development of existing and emerging targeted radiotherapeutics, which also poses a significant challenge in the discovery of new agents. Herein, we report the geometric and electronic structural properties of hydrated AcIII cations in the [AcIII(H2O) n ]3+ (n = 4-11) complexes in aqueous solution and gas-phase using density functional theory. We found that nine water molecules coordinated to the AcIII cation is the most stable complex due to an enhanced hydration Gibbs free energy. This complex adopts a closed-shell 18-electron configuration (1S 21P 61D 10) of a superatom state, which indicates a non-negligible covalent character and involves H2O → AcIII σ donation interaction between s-/p-/d-type atomic orbitals of the Ac atom and 2p atomic orbitals of the O atoms. Furthermore, potentially existing 10-coordinated complexes need to overcome an energy barrier (>0.10 eV) caused by hydrogen bonding to convert to 9-coordination. These results imply the importance of superatom states in actinide chemistry generally, and specifically in AcIII solution chemistry, and highlight the conversion mechanism between different coordination numbers.

Computational Characterization of AcIII-DOTA Complexes in Aqueous Solution.

The 1,4,7,10-tetrazacyclodecane-1,4,7,10-tetraacetic acid (DOTA) aqueous complexes of AcIII with H2O, dimethyl sulfoxide (DMSO), OH-, and F- as axial ligands were studied using density functional theory. Formation of the [AcIII(DOTA)(OH)]2- and [AcIII(DOTA)(F)]2- complexes is predicted to be significantly more favorable than that of [AcIII(DOTA)(H2O)]- and [AcIII(DOTA)(DMSO)]- because of the enhanced relative Gibbs free energies. Further electronic structure analyses demonstrate that the type and nature of the bond between Ac and the ligand donor atom is the main driving force that determines the thermodynamic stability of the complexes. Specifically, the [AcIII(DOTA)]- complex strongly binds to OH- and F- via covalent bonds, while the bonding to H2O and DMSO is ionic and relatively weaker.