Resonance Excitations in

The anomaly in lithium abundance is a well-known unresolved problem in nuclear astrophysics. A recent revisit to the problem tried the avenue of resonance enhancement to account for the primordial ^{7}Li abundance in standard big-bang nucleosynthesis. Prior measurements of the ^{7}Be(d,p)^{8}Be^{*} reaction could not account for the individual contributions of the different excited states involved, particularly at higher energies close to the Q value of the reaction. We carried out an experiment at HIE-ISOLDE, CERN to study this reaction at E_{c.m.}=7.8 MeV, populating excitations up to 22 MeV in ^{8}Be for the first time. The angular distributions of the several excited states have been measured and the contributions of the higher excited states in the total cross section at the relevant big-bang energies were obtained by extrapolation to the Gamow window using the talys code. The results show that by including the contribution of the 16.63 MeV state, the maximum value of the total S factor inside the Gamow window comes out to be 167 MeV b as compared to earlier estimate of 100 MeV b. However, this still does not account for the lithium discrepancy.

Ligand architectural effect on coordination, bonding, interaction, and selectivity of Am(iii) and Ln(iii) ions with bitopic ligands: synthesis, solvent extraction, and DFT studies.

The isolation of Am(iii) ion from Ln(iii) ions is very crucial for the safe disposal of nuclear wastes and thus, studies are being continuously pursued to accomplish this goal. In view of this, herein, a new conformationally rigid bitopic ligand, N,N,N',N'-tetra(2-ethylhexyl)piperazine-di-methylenecarboxamide (PIPDA) has been synthesized and studied for the separation of Am(iii) from Ln(iii) ions. The effect of structural rigidification on the selectivity of Am(iii) over Ln(iii) was compared with an open chain flexible compound, namely, N,N,N',N'-tetra(2-ethylhexyl)-3,6-(N'',N'''-dibutyl)diaza-octane-1,8-diamide (DADA). Two oxygen atoms of the diamide moiety seem to be responsible for controlling the metal ion extraction ability of PIPDA, whereas two nitrogen atoms of the piperazine moiety most probably dictate the separation factor between the Am(iii) and Eu(iii) ions in PIPDA. In addition, scalar relativistic density functional theory (DFT) in conjunction with Born-Haber thermodynamics was used herein to compliment the experimental selectivity. The experimentally observed preferential selectivity of PIPDA for Am(iii) ion over the Ln(iii) ion was corroborated by the computed extraction free energy, ΔGext. The covalent nature of bonding between the metal ions and the ligand was confirmed by analyzing the Mayer bond order and bond character analysis using the atom in molecule concept. Though the conformational rigidity of PIPDA gives stronger interaction than DADA, it does not offer a significant advantage over DADA in terms of the separation factor. The marginal increase in the separation factor for PIPDA over DADA might be attributed to the piperazine nitrogen and to the ligand architecture during complex formation.

DFT and MD simulation supplemented experiments for isotopic fractionation of zinc compounds using a macrocyclic crown ether appended polymeric resin.

Isotope effect is a quantum mechanical phenomenon and thus poses a challenge for the separation of isotopes of an element of interest, especially for heavy elements. Isotopic fractionation of zinc is also quite difficult and challenging but is necessitated due to various applications of its isotopes ranging from nuclear medicine to nuclear power reactors. Here, we developed the dibenzo-18-crown-6 (DB18C6) ether-functionalized poly(methacrylic acid) (PMA) resin by exploiting the ion and isotope recognition ability of the crown ether using DFT/MD simulations followed by experiments for isotopic fractionation of zinc. The PMADB18C6 adsorbent was prepared and suitably characterized. Both computational and experimental findings demonstrate that the adsorption and isotope separation of zinc with PMADB18C6 are due to the molecular recognition effect of the "O" dipole of the crown ether. Furthermore, both MD simulations and experiments suggest Langmuir type adsorption isotherms. The adsorption of Zn2+ ions on the PMA resin is predicted to be endothermic, whereas it is exothermic on the PMADB18C6 resin, as revealed from the experimentally observed enthalpy change. A small scale fixed bed column study was demonstrated to test the scale-up application. The values of the experimental separation factors: 1.0013 for 66/64 and 1.0027 for 68/64 confirm the computationally predicted results of 1.00088 and 1.0010, respectively, thus establishing the combined strength of the theory and experiments for the identification of efficient fractionating agents for a complex quantum isotope effect which eventually helps in planning further experiments in view of medicinal and technological applications of zinc isotopes.

Carbon nano tubes functionalized with novel functional group- amido-amine for sorption of actinides.

The manuscript presents the results on the sorption of U(VI), Am(III) & Eu(III) from pH medium by a novel amido-amine functionalized multiwalled carbon nanotube (MWCNT). The novel functional group was introduced in the MWCNT by two step processes and characterized by various instrumental techniques like Scanning Electron Microscopy (SEM), Raman and X-ray Photoelectron Spectroscopy (XPS). The sorption process was found to be highly dependent on the pH of the solution with maximum sorption for both 233U, 241Am & 152+154Eu at pH 7.0. Kinetics of sorption was found to be fast with equilibrium reached in ∼15min and the sorption was found to be following pseudo 2nd order kinetics for the radionuclides. The sorption for both 233U and 152+154Eu followed Langmuir sorption model with maximum sorption capacity of 20.66mg/g and 16.1mg/g respectively. This has been explained by DFT calculations which shows that more negative solvation energy of U(VI) compared to Am(III) and Eu(III) and stronger U-MWCNT-AA complex is responsible for higher sorption capacity of U(VI) compared to Am(III) and Eu(III).The synthesized amido-amine functionalized MWCNT is a very promising candidate for removal of actinides and lanthanides from waste water solution with high efficiency.

Complexation thermodynamics of diglycolamide with f-elements: solvent extraction and density functional theory analysis.

Comparative extraction of trivalent lanthanide and actinide ions (La(3+), Eu(3+), Lu(3+), Am(3+) and Cm(3+)) with tetra-n-octyl diglycolamide (TODGA) was studied and showed the trend: Lu(3+) > Eu(3+) > Cm(3+) > Am(3+) > La(3+). The structure, bonding, energetic and thermodynamic parameters of the trivalent lanthanide and actinide ions (La(3+), Eu(3+), Lu(3+), Am(3+) and Cm(3+)) with a tridentate ligand, tetra-methyl diglycolamide (TMDGA), are reported in the gas and solvent phases in order to understand their complexation and extraction behaviour. The calculations were performed using the generalized gradient approximated BP86 density functional and the hybrid B3LYP functional using SVP and TZVPP basis sets. The calculated structure obtained at the BP86/SVP level of optimization was found to be in close agreement with the X-ray data and also with the structure obtained at the B3LYP/TZVP level of theory. The free energy of extraction was found to be exergonic for the explicit monomer water model. From the solvent extraction experiment the order of extraction was observed as Lu(3+) > Eu(3+) > Cm(3+) > Am(3+) > La(3+), which was in line with the trends predicted based on the free energy changes in the gas phase calculations (ΔGgp). The Born-Haber thermodynamic cycle and the COSMO (conductor like screening model) solvation model were applied to calculate the free energy of extraction, ΔGext, of lanthanide and actinide ions in the aqueous-dodecane biphasic system and ΔGext, however, predicted different extraction trends. After dispersion correction (B3LYP-D3), the free energy of extraction for the metal ions was found to follow the order: Lu(3+) > Eu(3+) > La(3+), which was also observed in the solvent extraction experiments. Both COSMO and DCOSMO-RS models predict the same metal ion selectivity trend. Different bonding analyses indicate the electrostatic and less covalent nature of interactions between the ligands and the metal ions.

The entropic forces and dynamic integrity of single file water in hydrophobic nanotube confinements.

Water in nanotube exhibits remarkably different properties from the bulk phase, which can be exploited in various nanoconfinement based technologies. The properties of water within nanotube can be further tuned by varying the nanotube electrostatics and functionalization of nanotube ends. Here, therefore, we investigate the effect of quantum partial charges and carbon nanotube (CNT) termination in terms of associated entropic forces. An attempt has been made to correlate the entropic forces with various dynamical and structural properties. The simulated structural features are consistent with general theoretical aspects, in which the interfacial water molecules at H terminated CNT are found to be distributed in a different way as compared to other CNTs. The rotational entropy components for different cases of CNTs are well corroborated by the decay time of hydrogen bond (HB) correlation functions. A part of this event has been explained in terms of orientation of water molecules in the chain, i.e., the change in direction of dipole moment of water molecules in the chain and it has been revealed that the HBs of CNT confined water molecules show long preserving correlation if their rotations inside CNT are restricted. Furthermore, the translational entropy components are rationally integrated with the differing degree of translational constraints, added by the CNTs. To the best of our information, perhaps this is the first study where the thermodynamic effects introduced by H-termination and induced dipole of CNT have been investigated. Additionally, we present a bridge relation between "translational diffusivity and configurational entropy" for water transport from bulk phase to inside CNTs.

Thermodynamics of fluid conduction through hydrophobic channel of carbon nanotubes: the exciting force for filling of nanotubes with polar and nonpolar fluids.

Thermodynamic properties of the fluid in the hydrophobic pores of nanotubes are known to be different not only from the bulk phase but also from other conventional confinements. Here, we use a recently developed theoretical scheme of "two phase thermodynamic (2PT)" model to understand the driving forces inclined to spontaneous filling of carbon nanotubes (CNTs) with polar (water) and nonpolar (methane) fluids. The CNT confinement is found to be energetically favorable for both water and methane, leading to their spontaneous filling inside CNT(6,6). For both the systems, the free energy of transfer from bulk to CNT confinement is favored by the increased entropy (TΔS), i.e., increased translational entropy and increased rotational entropy, which were found to be sufficiently high to conquer the unfavorable increase in enthalpy (ΔE) when they are transferred inside CNT. To the best of our knowledge, this is the first time when it has been established that the increase in translational entropy during confinement in CNT(6,6) is not unique to water-like H bonding fluid but is also observed in case of nonpolar fluids such as methane. The thermodynamic results are explained in terms of density, structural rigidity, and transport of fluid molecules inside CNT. The faster diffusion of methane over water in bulk phase is found to be reversed during the confinement in CNT(6,6). Studies reveal that though hydrogen bonding plays an important role in transport of water through CNT, but it is not the solitary driving factor, as the nonpolar fluids, which do not have any hydrogen bond formation capacity can go inside CNT and also can flow through it. The associated driving force for filling and transport of water and methane is enhanced translational and rotational entropies, which are attributed mainly by the strong correlation between confined fluid molecules and availability of more free space for rotation of molecule, i.e., lower density of fluid inside CNT due to their single file-like arrangement. To the best of our information, this is perhaps the first study of nonpolar fluid within CNT using 2PT method. Furthermore, the fast flow of polar fluid (water) over nonpolar fluid (methane) has been captured for the first time using molecular dynamic simulations.

Structural and dynamical properties of Li+-dibenzo-18-crown-6(DB18C6) complex in pure solvents and at the aqueous-organic interface.

Microstructure of dibenzo-18-crown-6 (DB18C6) and DB18C6/Li(+) complex in different solvents (water, methanol, chloroform, and nitrobenzene) have been analyzed using radial distribution function (RDF), coordination number (CN), and orientation profiles, in order to identify the role of solvents on complexation of DB18C6 with Li(+), using molecular dynamics (MD) simulations. In contrast to aqueous solution of LiCl, no clear solvation pattern is found around Li(+) in the presence of DB18C6. The effect of DB18C6 has been visualized in terms of reduction in peak height and shift in peak positions of g(Li-Ow). The appearance of damped oscillations in velocity autocorrelation function (VACF) of complexed Li(+) described the high frequency motion to a "rattling" of the ion in the cage of DB18C6. The solvent-complex interaction is found to be higher for water and methanol due to hydrogen bond (HB) interactions with DB18C6. However, the stability of DB18C6/Li(+) complex is found to be almost similar for each solvent due to weak complex-solvent interactions. Further, Li(+) complex of DB18C6 at the liquid/liquid interface of two immiscible solvents confirm the high interfacial activity of DB18C6 and DB18C6/Li(+) complex. The complexed Li(+) shows higher affinity for water than organic solvents; still they remain at the interface rather than migrating toward water due to higher surface tension of water as compared to organic solvents. These simulation results shed light on the role of counter-ions and spatial orientation of species in pure and hybrid solvents in the complexation of DB18C6 with Li(+).

Density functional theoretical study on the preferential selectivity of macrocyclic dicyclohexano-18-crown-6 for Sr⁺² ion over Th⁺4 ion during extraction from an aqueous phase to organic phases with different dielectric constants.

The preferential selectivity of dicyclohexano-18-crown-6 (DCH18C6) for bivalent Sr(+2) ion over tetravalent Th(+4) ion was investigated using generalized gradient approximated (GGA) BP86 and the hybrid B3LYP density functional, employing split valence plus polarization (SV(P)) and triple-zeta valence plus polarization (TZVP) basis sets in conjunction with the COSMO (conductor-like screening model) solvation approach. The calculated theoretical selectivity of DCH18C6 for Sr(+2) ion over Th(+4) ion was found to be in accord with the selectivity for Sr(+2) ion over Th(+4) ion observed when performing liquid-liquid extraction experiments in different organic solvents. While 1:1(M:L) stoichiometric complexation reactions can be used to predict the preferential selectivity of Sr(2+) ion over Th(4+) ion, the results obtained are not consistent with the experimental results observed upon increasing the dielectric constant of the solvent. The calculated theoretical gas-phase data for the free energy of complexation, ∆G, fail to explain the selectivity for Sr(+2) ion over Th(+4) ion. However, when 1:2 (M:L) stoichiometric complexation reactions (reported in previous X-ray crystallography studies) are considered, correct and consistent results for the selectivity for Sr(+2) ion over a wide range of dielectric constants are predicted. The distribution constant for Sr(2+) and Th(4+) ions was found to gradually increase with increasing dielectric constant of the organic solvent, and was found to be highest in nitrobenzene. The selectivity data calculated from ∆∆G ext are in excellent agreement with the results obtained from solvent extraction experiments.

Microhydration of Cs+ ion: a density functional theory study on Cs+-(H2O)n clusters (n=1-10).

Structure, energy enthalpy, and IR frequency of hydrated cesium ion clusters, Cs+-(H2O)n (n=1-10), are reported based on all electron calculations. Calculations have been carried out with a hybrid density functional, namely, Becke's three-parameter nonlocal hybrid exchange-correlation functional B3LYP applying cc-PVDZ correlated basis function for H and O atoms and a split valence 3-21G basis function for Cs atom. Geometry optimizations for all the cesium ion-water clusters have been carried out with several possible initial guess structures following Newton-Raphson procedure leading to many conformers close in energy. The calculated values of binding enthalpy obtained from present density functional based all electron calculations are in good agreement with the available measured data. Binding enthalpy profile of the hydrated clusters shows a saturation behavior indicating geometrical shell closing in hydrated structure. Significant shifts of O-H stretching bands with respect to free water molecule in IR spectra of hydrated clusters are observed in all the hydrated clusters.