Electronic structure of spherical quantum dots using coupled cluster method

2, 6, 12, and 20 electron quantum dots have been studied using coupled cluster at singles and doubles level and extensive multireference coupled cluster (MRCC) method. A Fock-space version of MRCC (FSMRCC) containing single hole-particle excited determinants has been used to calculate low-lying excited states of the above system. The ionization potential and electron affinity are also calculated. The effect of correlation energy on excitation energy and charge density is shown by calculating them at the high density region (low value of density parameter rs) and at the low density region (high value of density parameter rs).     

Cu<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ni<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript> alloy nanoparticles embedded SiO<Subscript>2</Subscript> films: synthesis and structure

Cu–Ni fcc alloy nanoparticles (NPs) of tunable atomic ratios were generated in SiO₂ films. The films were prepared using the Cu(NO₃)₂ and Ni(NO₃)₂ co-doped inorganic–organic hybrid silica sols by single dipping. Transparent, crack-free, glassy SiO₂ films of 310 ± 10 nm in thickness embedded with high mol percent of Cu–Ni alloy NPs were yielded after annealing at 750 °C in 10% H₂-90% Ar atmosphere. Nominal compositions of the films were 20 mol% (Cu–Ni)-80 mol% SiO₂. Optical spectral study of the heat-treated films showed disappearance of Cu plasmon bands due to Cu–Ni alloy formation. Grazing incidence X-ray diffraction (GIXRD) studies revealed the formation of Cu–Ni alloy (2:1, 1:1 and 1:2) NPs inside the SiO₂ film. GIXRD showed a systematic shifting of the diffraction peaks with respect to the fcc Cu–Ni alloy composition, maintaining the nominal ratios. Transmission electron microscopy (TEM) studies of the representative Cu_0.5Ni_0.5-doped film showed existence of homogeneously dispersed Cu–Ni alloy NPs of average size 6.35 nm inside the SiO₂ matrix. The energy dispersive X-ray scattering (EDX) analysis of the individual NPs using the nano-probe (scanning TEM mode) confirmed the presence of both the Cu and Ni with the desired atomic ratio.     

Sonochemical synthesis and application of rhodium–graphene nanocomposite

Abstract  

Highly water dispersible rhodium–graphene nanocomposite have been successfully synthesized by the simple reduction of Rh³⁺ salt on poly(ethylene oxide)/poly(propylene oxide)/poly(ethylene oxide) (PEO/PPO/PEO) triblock copolymer or pluronic-stabilized graphene oxide (GO) nanosheets with borohydride. Rhodium nanoparticles, having average size of 1–3 nm, are homogeneously distributed through out the graphene sheets. Some porous structures of graphene sheets have also been observed after the reduction of pluronic-stabilized GO in the presence of metal ions. The material is very effective for hydrogenation of arenes, especially for benzene as the substrate material at the room temperature and 5 atm pressure of hydrogen.     

Fabrication of multi-structure nanocarbons from carbon xerogel: a unique scaffold towards bio-imaging

A novel route has been developed to fabricate different carbon nanostructures having individual morphology of carbon nanoparticles: nanofullerene, nanocube, nanoleaf and porous nanorods, through the combustion of carbon xerogel with nitric acid. These fabricated nanostructures exhibited bright green fluorescence under the exposure of UV light.     

An Interplay of Cooperativity between Cation⋅⋅⋅π, Anion⋅⋅⋅π and C?H⋅⋅⋅Anion Interactions

Mixed cation (Li⁺, Na⁺ and K⁺) and anion (F^?, Cl^?, Br^?) complexes of the aromatic π‐surfaces (top and bottom) are studied by using dispersion‐corrected density functional theory. The selectivity of the aromatic surface to interact with a cation or an anion can be tuned and even reversed by the electron‐donating/electron‐accepting nature of the side groups. The presence of a methyl group in the ? OCH₃, ? SCH₃, ? OC₂H₅ in the side groups of the aromatic ring leads to further cooperative stabilization of the otherwise unstable/weakly stable anion???π complexes by bending of the side groups towards the anion to facilitate C? H???anion interactions. The cooperativity among the interactions is found to be as large as 100 kcal mol^?1 quantified by dissection of the three individual forces from the total interaction energy. The crystal structures of the fluoride binding tripodal and hexapodal ligands provide experimental evidence for such cooperative interactions.     

Electrically Conductive π-Intercalated Graphitic Metal-Organic Framework Containing Alternate π-Donor/Acceptor Stacks

Two-dimensional graphitic metal–organic frameworks (GMOF) often display impressive electrical conductivity chiefly due to efficient through-bond in-plane charge transport, however, less efficient out-of-plane conduction across the stacked layers creates large disparity between two orthogonal conduction pathways and dampens their bulk conductivity. To address this issue and engineer higher bulk conductivity in 2D GMOFs, we have constructed via an elegant bottom-up method the first π-intercalated GMOF (iGMOF1) featuring built-in alternate π-donor/acceptor (π-D/A) stacks of Cu^II-coordinated electron-rich hexaaminotriphenylene (HATP) ligands and non-coordinatively intercalated π-acidic hexacyano-triphenylene (HCTP) molecules, which facilitated out-of-plane charge transport while the hexagonal Cu₃(HATP)₂ scaffold maintained in-plane conduction. As a result, iGMOF1 attained an order of magnitude higher bulk electrical conductivity and much smaller activation energy than Cu₃(HATP)₂ (σ=25 vs. 2 S m⁻¹, E_a=36 vs. 65 meV), demostrating that simultaneous in-plane (through-bond) and out-of-plane (through πD/A stacks) charge transport can generate higher electrical conductivity in novel iGMOFs.     

Strategic Synthesis of Heptacoordinated FeIII Bifunctional Complexes for Efficient Water Electrolysis

In this research, highly efficient heterogeneous bifunctional (BF) electrocatalysts (ECs) have been strategically designed by Fe coordination (C_R) complexes, [Fe₂L₂(H₂O)₂Cl₂] (C1) and [Fe₂L₂(H₂O)₂(SO₄)].2(CH₄O) (C2) where the high seven C_R number synergistically modifies the electronic environment of the Fe centre for facilitation of H₂O electrolysis. The electronic status of Fe and its adjacent atomic sites have been further modified by the replacement of −Cl⁻ in C1 by −SO₄²⁻ in C2 . Interestingly, compared to C1 , the O−S−O bridged C2 reveals superior BF activity with extremely low overpotential (η) at 10 mA cm⁻² (140 mV_OER, 62 mV_HER) and small Tafel slope (120.9 mV dec⁻¹_OER, 45.8 mV dec⁻¹_HER). Additionally, C2 also facilitates a high-performance alkaline H₂O electrolyzer with cell voltage of 1.54 V at 10 mA cm⁻² and exhibits remarkable long-term stability. Thus, exploration of the intrinsic properties of metal–organic framework (MOF)-based ECs opens up a new approach to the rational design of a wide range of molecular catalysts.     

Multichromophoric dye-sensitized solar cells based on supramolecular zinc-porphyrinperylene-imide dyads

Multichromophoric dye-sensitized solar cells (DSCs) based on self-assembled zinc-porphyrinperyleneimide dyads on TiO(2) films display more efficient light-to-electrical energy conversion than DSCs based on individual dyes. Higher efficiency of multichromophoric dyes can be attributed to co-sensitization as well as vectorial electron transfer that lead to better electron-hole separation in the device.     

Fabrication of magnetically separable palladium–graphene nanocomposite with unique catalytic property of hydrogenation

One step solvothermal route has been developed to prepare a well dispersed magnetically separable palladium–graphene nanocomposite, which can act as a unique catalyst against hydrogenation due to the uniform decoration of palladium nanoparticles throughout the surface of the magnetite–graphene nanocomposite and hence can be reused for several times. In addition to catalytic activity, palladium nanoparticles also facilitate the formation and homogeneous distribution of magnetite (Fe₃O₄) nanoparticles onto the graphene surfaces or else an agglomerated product has been obtained after the solvothermal reduction of graphene oxide in presence of Fe³⁺ alone.