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The geometry of the neutral Au18 gold cluster was probed by a combination of quantum chemical calculations and far-infrared multiple photon dissociation (FIR-MPD) spectroscopy of a Kr messenger complex.

I2-promoted synthesis of BIMPYs.

The onset of the transition from 2D to 3D structures in pure gold clusters remains a matter of continuing debates. In this study we revisited several planar and non-planar structural motifs of the size Au10 with the aim to clarify this issue. Computations using a long-range corrected exchange-correlation functional LC-BLYP, coupled-cluster theories CCSD(T) and PNO-LCCSD(T)-F12 revealed that, at variance with previous reports on the preference of a planar elongated hexagon, both planar and nonplanar isomers of the neutral Au10 are energetically degenerated up to 300K. Its 3D equilibrium geometry is a core-shell structure which can be built up from a trigonal prism by capping four extra Au atoms outside. A comparison to the available experimental vibrational spectra allowed us to argue that both 2D and 3D isomers of the Au10 likely coexist in the molecular beam during the measurement of its FIR spectra. This results also suggests that the 2D-3D transition of neutral gold clusters occurs at the size Au10.

B56 a system with a magenetic ring current that flows in the opposite direction of most of the aromatic systems.

The Au17 gold cluster was experimentally produced in the gas phase and characterized by its vibrational spectrum recorded using far-IR multiple photon dissociation (FIR-MPD) of Au17Kr. DFT and coupled-cluster theory PNO-LCCSD(T)-F12 computations reveal that, at odds with most previous reports, Au17 prefers two star-like forms derived from a pentaprism added by two extra Au atoms on both top and bottom surfaces of the pentaprism, along with five other Au atoms each attached on a lateral face. A good agreement between calculated and FIR-MPD spectra indicates a predominant presence of these star-like isomers. Stabilization of a star form arises from strong orbital interactions of an Au12 core with a five-Au-atom string.

A theoretical study of geometric and electronic structures, stability and magnetic properties of both neutral and anionic Ge16M0/- clusters with M being a first-row 3d transition metal atom, is performed using quantum chemical approaches. Both the isoelectronic Ge16Sc- anion and neutral Ge16Ti that have a perfect Frank-Kasper tetrahedral T d shape and an electron shell filled with 68 valence electrons, emerge as magic clusters with an enhanced thermodynamic stability. The latter can be rationalized by the simple Jellium model. Geometric distortions from the Frank-Kasper tetrahedron of Ge16M having more or less than 68 valence electrons can be understood by a Jahn-Teller effect. Remarkably, DFT calculations reveal that both neutral Ge16Sc and Ge16Cu can be considered as superhalogens as their electron affinities (≥3.6 eV) exceed the value of the halogen atoms and even that of icosahedral Al13. A detailed view of the magnetic behavior of Ge16M0/- clusters shows that the magnetic moments of the atomic metals remain large even when they are quenched upon doping. When M goes from Sc to Zn, the total spin magnetic moment of Ge16M0/- increases steadily and reaches the maximum value of 3 μ B with M = Mn before decreasing towards the end of the first-row 3d block metals. Furthermore, the IR spectra of some tetrahedral Ge16M are also predicted. ispartof: RSC Adv vol:12 issue:21 pages:13487-13499 ispartof: location:England status: Published online

Hydrogen bonds (H-bonds) in the complexes between aldehydes and hydrogen chalcogenides, XCHO...nH2Z with X = H, F, Cl, Br, and CH3, Z = O, S, Se, and Te, and n = 1,2, were investigated using high-level ab initio calculations. The Csp2-H...O H-bonds are found to be about twice as strong as the Csp2-H...S/Se/Te counterparts. Remarkably, the S/Se/Te-H...S/Se/Te H-bonds are 4.5 times as weak as the O-H...O ones. The addition of the second H2Z molecule into binary systems induces stronger complexes and causes a positive cooperative effect in ternary complexes. The blue shift of Csp2-H stretching frequency involving the Csp2-H...Z H-bond sharply increases when replacing one H atom in HCHO by a CH3 group. In contrast, when one H atom in HCHO is substituted with a halogen, the magnitude of blue-shifting of the Csp2-H...Z H-bond becomes smaller. The largest blue shift up to 92 cm-1 of Csp2-H stretching frequency in Csp2-H...O H-bond in CH3CHO...2H2O has rarely been observed and is much greater than that in the cases of the Csp2-H...S/Se/Te ones. The Csp2-H blue shift of Csp2-H...Z bonds in the halogenated aldehydes is converted into a red shift when H2O is replaced by a heavier analogue, such as H2S, H2Se, or H2Te. The stability and classification of nonconventional H-bonds including Csp2-H...Se/Te, Te-H...Te, and Se/Te-H...O have been established for the first time.

Structures of B70 in both neutral and dianionic states were reinvestigated using genetic search, leapfrog path and DFT computations. The quasi-planar form of the B702− dianion possesses 50 π-electrons that satisfy disk aromaticity count and make it the most stable isomer.

The structures of cationic CrSin+ (n = 6–10) clusters were determined by complementary experimental and computation work. Some of the clusters were found to have pairs of enantiomeric isomers.

Surface-enhanced Raman spectroscopy (SERS) was employed to gain an understanding of the chemical enhancement mechanism of 2,4,5-trichlorophenoxyacetic acid (2,4,5-T), an Agent Orange, adsorbed on a silver substrate surface. Experimental measurements were performed using a micro-Raman spectrophotometer with an excitation wavelength of 532 nm and successfully detected 2,4,5-T at a relatively low concentration of 0.4 nM. Density functional theory (DFT) calculations on the interactions of the 2,4,5-T molecule with some small silver clusters, Agn with n = 4, 8, and 20, as well as with extended Ag surfaces, demonstrate that the most stable adsorption configuration is formed via coordination of Cl9 sites and carbonyl C═O group on the 2,4,5-T ligand to the Ag atoms on surfaces. Analyses of charge transfer mechanism and frontier orbitals distributions show an electron transfer from 2,4,5-T to the cluster in the ground state, and an inversed trend occurs for the excited singlet state process, consequently leading to a chemical enhancement of SERS signals. The obtained results are of importance for subsequent work in guiding the design of mobile sensors specifically used for services of rapid screening and detection of these toxic compounds present in the environment, as well as agricultural and food products. Extensive computations pointed out that small silver clusters, in particular of Ag20 size, can be used as appropriate models for a metal nanoparticle surface.

The lowest-lying isomer of the B50 boron cluster is confirmed to have a quasi-planar shape with two hexagonal holes. By applying a topological (leap-frog) dual operation followed by boron capping, we demonstrated that such a quasi-planar structure actually comes from the smallest elongated B102-, and its high thermodynamic stability is due to its inherent disk aromaticity arising from its 32 valent π electrons that fully occupy a disk configuration of [(1σ)2(1π)4(1δ)4(2σ)2(1φ)4(2π)4(1γ)4(2δ)4(1η)4]. The aromatic character of the quasi-planar B50 is further supported by a strong diatropic magnetic current flow. The sudden appearance of a quasi-planar B50 again points out that the growth pattern of pure boron clusters is still far from being completely understood.

Quantum chemical computations using both density functional theory and coupled-cluster theory methods, in conjunction with a polarizable continuum model for treatment of structures in solution, were carried out on a series of small water anions [(H2O)n]•־, n = 2, 3, 4, 5, and 16. Location of the excess electron was probed from a partition of electron densities using ELF and AIM techniques. For each size n of the [(H2O)n]•־ system, two distinct structural motifs are identified: a classical water radical anion formed by hydrogen bonds and a hydrated electron in which the excess electron is directly interacting with H atoms. Both motifs have comparable energy content and likely coexist in aqueous solution.

Transport properties of the halogeno-alkali oxides A3OX (A = Li, Na, X = Cl, Br) nanocrystalline samples with the presence of ∑3(111) grain boundaries were computed using large-scale molecular dynamic simulations. Results on the diffusion/conduction process show that these nanocrystalline samples are characterized with higher activation energies as compared to previous theoretical studies, but closer to experiment. Such a performance can be attributed to the larger atomic density at the ∑3(111) grain boundary regions within the nanocrystals. Despite a minor deterioration of transport properties of the mixed cation Li2NaOX and Na2LiOX samples, these halogeno-alkali oxides can also be considered as good inorganic solid electrolytes in both Li- and Na-ion batteries. ispartof: RSC Adv vol:12 issue:31 pages:20029-20036 ispartof: location:England status: Published online

Transport properties of the halogeno-alkali oxides A

The small binary boron silicon clusters B

The improvement of Li-ion transport properties and doping engineering in Li-ion batteries are currently active research topics in the search for next-generation energy storage devices. In this theoretical work, the intrinsic defect formation and transport properties of divalent metal-doped Li2SnO3, which is being considered as an electrode and coating electrode material, are explored using atomistic simulations. Defect formation simulations reveal that all divalent dopants (Zn, Sc, Cd and Eu) occupy the Li site with charge compensation through Li vacancies. Molecular dynamics simulations show that the divalent dopants significantly reduce the activation energy for ionic diffusion and conduction compared to the undoped sample. The effects of both grains and grain boundaries on the Li-ion transport properties are investigated. Our calculated results demonstrate a marked improvement in the properties of Li2SnO3 that can be achieved either in current commercial and next-generation Li-ion battery technologies through divalent doping in mono- and polycrystalline Li2SnO3 samples.

A recent paper by Rodriguez-Kessler et al., Phys. Chem. Chem. Phys., 2020, 22, 27255–27262, reported not only results of quantum chemical computations (using the PW91 density functional) on Ag16 clusters as emphasized in the article's title, but also on the Ag15 size. These authors confirmed previous results obtained by McKee and Samokhvalov (J. Phys. Chem. A, 2017, 121, 5018–5028 using the M06 density functional) that the most stable isomer of Ag15 is a C2v structure. We wish to point out that two low symmetry isomers of Ag15 that have a similar energy content are even lower in energy than their reported C2v global minimum. The relative energies between low-lying Ag15 isomers were again found to be method-dependent, and within the expected accuracy of DFT and CCSD(T) methods they could be considered as energetically degenerate, and likely coexist in a molecular beam. The new lower-energy Ag15 isomers appear to fit more consistently within the structural evolution of small silver clusters.

Molecular structures and properties of the binary clusters containing twelve boron atoms mixed with n lithium atoms, B12Lin with n = 1–14, were investigated using density functional theory with the TPSSh functional and the 6-311+G(d) basis set. Energetic parameters including relative energies, average binding energies and second-order energies of the entire series were predicted using the coupled-cluster theory (U)CCSD(T) in conjunction with the cc-pVTZ basis set. Several lowest-lying isomers were determined for each size B12Lin whose energies differ from each other by

Reduction of phosphorus dichloride 6, supported by the diaryloxyphenyl group (OCO) featuring two bulky phenoxy wingtips, by PMe3, generates a reactive intermediate that behaves as a base-stabilized phosphinidene (OCO)P (5). Warming up a solution of this species in toluene to room temperature results in trimerization to give the isolable cyclic triphosphine [(OCO)P]3, whereas in situ trapping with 2,3-dimethylbutadiene-1,3 afforded a 3,4-dimethylphospholene-3. Investigation of the reduction of 6 by the phosphine PMe3 by NMR led to the observation of a persistent species between -10 °C and 10 °C. DFT study of this process suggest that this compound cannot be the proposed phosphinidene 5, and is more likely the disphosphine (OCO)ClP-PCl(OCO) (12). Attempted reduction of 5 by the bulky carbene IPr resulted in unusual electrophilic substitution in the carbene olefin backbone by the chlorophosphinyl group.

Pramipexole (PPX) is known in the treatment of Parkinson's disease and restless legs syndrome. We carried out a theoretical investigation on pramipexole-Au cluster interactions for the applications of drug delivery and detection. Three Au N clusters with sizes N = 6, 8 and 20 were used as reactant models to simulate the metallic nanostructured surfaces. Quantum chemical computations were performed in both gas phase and aqueous environments using density functional theory (DFT) with the PBE functional and the cc-pVDZ-PP/cc-pVTZ basis set. The PPX drug is mainly adsorbed on gold clusters via its nitrogen atom of the thiazole ring with binding energies of ca. -22 to -28 kcal mol-1 in vacuum and ca. -18 to -24 kcal mol-1 in aqueous solution. In addition to such Au-N covalent bonding, the metal-drug interactions are further stabilized by electrostatic effects, namely hydrogen-bond NH⋯Au contributions. Surface-enhanced Raman scattering (SERS) of PPX adsorbed on the Au surfaces and its desorption process were also examined. In comparison to Au8, both Au6 and Au20 clusters undergo a shorter recovery time and a larger change of energy gap, being possibly conducive to electrical conversion, thus signaling for detection of the drug. A chemical enhancement mechanism for SERS procedure was again established in view of the formation of nonconventional hydrogen interactions Au⋯H-N. The binding of PPX to a gold cluster is expected to be reversible and triggered by the presence of cysteine residues in protein matrices or lower-shifted alteration of environment pH. These findings would encourage either further theoretical probes to reach more accurate views on the efficiency of pramipexole-Au interactions, or experimental attempts to build appropriate gold nanostructures for practical trials, harnessing their potentiality for applications. ispartof: RSC Adv vol:11 issue:27 pages:16619-16632 ispartof: location:England status: Published online

Understanding of the abiotic formation of nucleosides under geochemical conditions is currently a major scientific challenge. In this study, free radical pathways for formation of RNA nucleosides with canonical nucleobases are proposed for the first time. The pathways proceed with relatively low energy barriers for the formation of ribose as well as all RNA nucleosides. The formose reaction proceeds either with or without Ca2+ and CaOH+ cations. An autocalytic cycle for the formation of both glycolaldehyde and glyceraldehyde is identified when Ca2+ or CaOH+ cations are involved in the reaction. The results suggest that Ca2+ cations are not involved in the formation of ribose from glyceraldehyde. In addition, these pathways lead to the formation of dihydroxyacetone and d-erythrose. Calculated results show that the glycosidic bond can be formed abiotically between the d-ribose and the nucleobase, where d-ribose forms a cyclic free radical that subsequently reacts with the neutral nucleobase. Involvement of proper nucleobase tautomer is important for the formation of RNA nucleosides. Our approaches provide a solution for the long-standing question of how the glycosidic bond is formed under the abiotic conditions with low energy barriers. The pathways for formation of the sugars without a catalyst are relevant to the formation of sugars in interstellar clouds. On the other hand, the autocalysis in the formose reaction followed by the formation of the nucleosides is appropriate for the abiotic synthesis taking place in the presence of water in the early Earth environment. The Ca2+ and CaOH+ cations appear to be the first nonenzymatic catalytic systems for formation of biomolecules.

The first trefoil leaf-shaped cluster, a novel structural motif, was discovered by quantum chemical computations using density functional theory methods for both binary M3@E20 silicon and germanium...