Ab initio and density functional theoretical design and screening of model crown ether based ligand (host) for extraction of lithium metal ion (guest): effect of donor and electronic induction

2012 ◽  
Vol 18 (8) ◽  
pp. 3507-3522 ◽  
Author(s):  
Anil Boda ◽  
Sk. Musharaf Ali ◽  
Hanmanth Rao ◽  
Sandip K. Ghosh
Keyword(s):  
Crown Ether ◽  
Ab Initio ◽  
Metal Ion ◽  
Density Functional ◽  
Lithium Metal ◽  
Theoretical Design

scholarly journals EXTRACTION OF STRONTIUM(II) BY CROWN ETHER: INSIGHTS FROM DENSITY FUNCTIONAL CALCULATION

2012 ◽  
Vol 12 (3) ◽  
pp. 207-216 ◽  
Author(s):  
Saprizal Hadisaputra ◽  
Harno Dwi Pranowo ◽  
Ria Armunanto
Keyword(s):  
Crown Ether ◽  
Organic Solvent ◽  
Interaction Energy ◽  
Thermodynamic Parameters ◽  
Metal Ion ◽  
Density Functional ◽  
Pure Water ◽  
Density Functional Method ◽  
Basis Set ◽  
Solvent Phase

The structures, energetic and thermodynamic parameters of crown ethers with different cavity size, electron donating/withdrawing substituent groups and donor atoms have been determined with density functional method at B3LYP level of theory in gas and solvent phase. Small core quasi-relativistic effective core potentials was used together with the accompanying SDD basis set for Sr2+ and DZP basis set was used for crown ether atoms. Natural bond orbital (NBO) analysis was evaluated to characterize the distribution of electrons on the complexes. The interaction energy is well correlated with the values of Strontium charge after complexation, the second order interaction energies (E2) and HOMO-LUMO energy gab (∆Egab). The interaction energy and thermodynamics parameters in gas phase are reduced in solvent phase as the solvent molecules weaken the metal-crown ether interaction. The thermodynamic parameters indicated that less feasibility to extract Sr2+ ion directly from pure water without presence of organic solvent. The theoretical values of extraction energy for Sr(NO3)2 salt from aqueous solution in different organic solvent is validated by the experimental trend. This study would have strong contribution in planning the experiments to the design of specific host ligand and screening of solvent for extraction of metal ion.

A Combined ab initio and Density Functional Study of the Electronic Structure of Thymine and 2-Thiothymine Radicals

2003 ◽  
Vol 68 (12) ◽  
pp. 2322-2334 ◽  
Author(s):  
Robert Vianello ◽  
Zvonimir B. Maksić
Keyword(s):  
Ab Initio ◽  
Spin Density ◽  
Density Functional ◽  
Radical Cations ◽  
Functional Study ◽  
Theory Approach ◽  
Functional Theory ◽  
Adiabatic Ionization Potential ◽  
Highest Occupied Molecular Orbital ◽  
Positively Charged

The electronic and energetic properties of thymine (1) and 2-thiothymine (2) and their neutral and positively charged radicals are considered by a combined ab initio and density functional theory approach. It is conclusively shown that ionization of 1 and 2 greatly facilitates deprotonation of the formed radical cations thus making the proton transfer between charged and neutral precursor species thermodynamically favourable. The adiabatic ionization potential of 1 and 2 are analysed. It appears that ADIP(1) is larger than ADIP(2) by 10 kcal/mol, because of greater stability of the highest occupied molecular orbital (HOMO) of the former. It is also shown beyond any doubt that the spin density in neutral and cationic radical of 2 is almost exclusively placed on the σ-3p AO of sulfur implying that these two systems represent rather rare sigma-radicals. In contrast, the spin density of radicals of 1 is distributed over their π-network.

PEO-based electrolytes blended with star polymers with precisely imprinted polymeric pseudo-crown ether cavities for alkali metal ion batteries

2019 ◽  
Vol 576 ◽  
pp. 182-189 ◽  
Author(s):  
Zhuliu Xiao ◽  
Binghua Zhou ◽  
Jirong Wang ◽  
Cai Zuo ◽  
Dan He ◽  
...  
Keyword(s):  
Crown Ether ◽  
Alkali Metal ◽  
Metal Ion ◽  
Star Polymers ◽  
Alkali Metal Ion

scholarly journals Phonons in Short-Period GaN/AlN Superlattices: Group-Theoretical Analysis, Ab initio Calculations, and Raman Spectra

Nanomaterials ◽  
2021 ◽  
Vol 11 (2) ◽  
pp. 286
Author(s):  
Valery Davydov ◽  
Evgenii Roginskii ◽  
Yuri Kitaev ◽  
Alexander Smirnov ◽  
Ilya Eliseyev ◽  
...  
Keyword(s):  
Theoretical Analysis ◽  
Ab Initio Calculations ◽  
Ab Initio ◽  
Raman Spectra ◽  
Density Functional ◽  
Structural Characteristics ◽  
Vibrational Modes ◽  
Phonon Modes ◽  
Short Period ◽  
Group Theoretical Analysis

We report the results of experimental and theoretical studies of phonon modes in GaN/AlN superlattices (SLs) with a period of several atomic layers, grown by submonolayer digital plasma-assisted molecular-beam epitaxy, which have a great potential for use in quantum and stress engineering. Using detailed group-theoretical analysis, the genesis of the SL vibrational modes from the modes of bulk AlN and GaN crystals is established. Ab initio calculations in the framework of the density functional theory, aimed at studying the phonon states, are performed for SLs with both equal and unequal layer thicknesses. The frequencies of the vibrational modes are calculated, and atomic displacement patterns are obtained. Raman spectra are calculated and compared with the experimental ones. The results of the ab initio calculations are in good agreement with the experimental Raman spectra and the results of the group-theoretical analysis. As a result of comprehensive studies, the correlations between the parameters of acoustic and optical phonons and the structure of SLs are obtained. This opens up new possibilities for the analysis of the structural characteristics of short-period GaN/AlN SLs using Raman spectroscopy. The results obtained can be used to optimize the growth technologies aimed to form structurally perfect short-period GaN/AlN SLs.

Ab Initio Calculation of Mechanical Properties of Stacking Fault in 3C-SiC: Effect of Stress and Doping

2012 ◽  
Vol 717-720 ◽  
pp. 415-418
Author(s):  
Yoshitaka Umeno ◽  
Kuniaki Yagi ◽  
Hiroyuki Nagasawa
Keyword(s):  
Mechanical Properties ◽  
Ab Initio ◽  
Density Functional ◽  
Stacking Faults ◽  
Single Layer ◽  
Local Strain ◽  
Density Functional Theory Calculations ◽  
Stacking Fault ◽  
Functional Theory ◽  
N Doping

We carry out ab initio density functional theory calculations to investigate the fundamental mechanical properties of stacking faults in 3C-SiC, including the effect of stress and doping atoms (substitution of C by N or Si). Stress induced by stacking fault (SF) formation is quantitatively evaluated. Extrinsic SFs containing double and triple SiC layers are found to be slightly more stable than the single-layer extrinsic SF, supporting experimental observation. Effect of tensile or compressive stress on SF energies is found to be marginal. Neglecting the effect of local strain induced by doping, N doping around an SF obviously increase the SF formation energy, while SFs seem to be easily formed in Si-rich SiC.

scholarly journals H2O coordination in macropa complexes of f elements (Ac, La, Lu): feasibility of the 11th coordination site

2021 ◽  
Author(s):  
Attila Kovács ◽  
Zoltán Varga
Keyword(s):  
Aqueous Solution ◽  
Metal Ion ◽  
Density Functional ◽  
Molecular Level ◽  
Density Functional Theory Calculations ◽  
Functional Theory ◽  
Coordination Site ◽  
Additional Ligand ◽  
Ligand Coordination ◽  
Bonding Properties

AbstractThe feasibility of an additional ligand coordination at the 11th coordination site of actinium, lanthanum, and lutetium ions in 10-fold coordinated macropa complexes has been studied by means of density functional theory calculations. The study covered the two main macropa conformers, Δ(δλδ)(δλδ) and Δ(λδλ)(λδλ), favoured by larger (Ac3+, La3+) and smaller (Lu3+) ions, respectively. At the molecular level, the coordination of H2O is the most favourable to the largest Ac3+ while only slightly less to La3+. Protonation of the picoline arms enhances the coordination by shifting the metal ion closer to the open site of the ligand. The choice of macropa conformer has only a slight influence on the strength and bonding properties of the H2O coordination. Aqueous solution environment decreases considerably the energy gain of H2O coordination at the 11th coordination site.

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