Design, Synthesis, and Structural Characterization of a Bisantimony(III) Compound for Anion Binding and the Density Functional Theory Evaluation of Halide Binding through Antimony Secondary Bonding Interactions

2016 ◽  
Vol 120 (46) ◽  
pp. 9257-9269 ◽  
Author(s):  
Jinchun Qiu ◽  
Daniel K. Unruh ◽  
Anthony F. Cozzolino
Keyword(s):  
Density Functional Theory ◽  
Structural Characterization ◽  
Density Functional ◽  
Anion Binding ◽  
Functional Theory ◽  
Design Synthesis ◽  
Theory Evaluation ◽  
The Density Functional Theory ◽  
Secondary Bonding

Density functional theory (DFT) calculations on the structures and stabilities of [CnO2n+1]2– and [CnO2n+1]X2 polycarbonates containing chainlike (CO2)n units (n = 2–6; X = H or Li)

2011 ◽  
Vol 89 (6) ◽  
pp. 671-687 ◽  
Author(s):  
Pablo J. Bruna ◽  
Friedrich Grein ◽  
Jack Passmore
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Ion Pairs ◽  
Dicarboxylic Acids ◽  
Polarizable Continuum Model ◽  
Weakly Bound ◽  
Functional Theory ◽  
The Density Functional Theory ◽  
Weakly Bound Complexes

The structures and stabilities of chainlike (CO2)n (n = 2–6) polycarbonates, where adjacent C atoms are linked by C–O–C bonds, were investigated at the density functional theory (DFT) level (B3PW91/6–311G(2d,p)), including dicarboxylic dianions, [CnO2n+1]2–, and the corresponding acids, [CnO2n+1]H2, and Li salts, [CnO2n+1]Li2. At equilibrium, the most stable systems have Cs, C2, or C2v symmetries. In the gas phase, these dianions are generally metastable with respect to spontaneous ejection of one electron, yet in the presence of counterions they become stabilized, for example, as [CnO2n+1]2–(Li+)2 ion pairs. [CnO2n+1]2– linkages are also stabilized as dicarboxylic acids, [CnO2n+1]H2; we find the latter to have equilibrium conformations of higher symmetry than previously reported in the literature. To the best of our knowledge, none of the [CnO2n+1]X2 (X = Li or H) compounds with n ≥ 2 have been reported in the experimental literature (albeit, the alkyl esters C2O5R2 and C3O7R2 are commercially available). All CO bonds in C2O5X2 to C6O13X2 have single- to double-bond character (≈140–118 pm), indicating that the [CnO2n+1] moieties are held together by strong chemical forces (in contrast to the weakly bound complexes (CO2)n and (CO2)n–, n > 1). Vibrational frequencies were calculated to ensure all conformations were true minima. The IR and Raman intensities show that the high intensity C=O stretching modes (1750 ± 100 cm–1) will help in the spectral characterization of these compounds. Solvation calculations using the polarizable continuum model (PCM) find that C2O52– can be formed via CO32– + CO2 as well as CO3–[Formula: see text], each reaction having ΔG298 < 0 in practically all solvents. This result confirms the experimentally observed large solubility of CO2(g) in molten carbonates, CO3M2 (M = Li, Na, or K). In contrast, starting with n = 2, the reactions [CnO2n+1]2– + CO2 do not proceed spontaneously in any solvent (ΔG298 > 0).

Design and structural characterization of the all-metal aromatic sandwich species [Bi3Au3Bi3]3−: insight from density functional theory

2017 ◽  
Vol 41 (6) ◽  
pp. 2321-2327 ◽  
Author(s):  
Li-Hong Tang ◽  
Ting-Ting Zhu ◽  
Ping Ning ◽  
Kai Li ◽  
Shuang-You Bao ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Structural Characterization ◽  
Density Functional ◽  
Functional Theory ◽  
Aromatic Structure

The [Bi3Au3Bi3]3− species, with hollow features, has a unique all-metal sandwich aromatic structure.

scholarly journals Hydrosilyation of CO2 using a silatrane hydride: structural characterization of a silyl formate compound

2021 ◽  
Vol 99 (2) ◽  
pp. 259-267
Author(s):  
Serge Ruccolo ◽  
Erika Amemiya ◽  
Daniel G. Shlian ◽  
Gerard Parkin
Keyword(s):  
Molecular Structure ◽  
Density Functional Theory ◽  
Oxygen Atom ◽  
Structural Characterization ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
X Ray Diffraction ◽  
Functional Theory ◽  
X Ray

The silatrane hydride compound, [N(CH2CH2O)3]SiH, reacts with CO2 in the presence of the [tris(2-pyridylthio)methyl]zinc hydride complex, [Tptm]ZnH, to afford the silyl formate and methoxide derivatives, [N(CH2CH2O)3]SiO2CH and [N(CH2CH2O)3]SiOCH3. The molecular structure of [N(CH2CH2O)3]SiO2CH has been determined by X-ray diffraction, thereby demonstrating that the formate ligand adopts a distal conformation in which the uncoordinated oxygen atom resides with a trans-like disposition relative to silicon. Density functional theory calculations indicate that the atrane motif of [N(CH2CH2O)3]SiO2CH is flexible, such that the energy of the molecule changes relatively little as the Si···N distance varies over the range 2.0–3.0 Å.

Density Functional Theory Investigation and Detonation Characterization of DNPDNAZ

2014 ◽  
Vol 997 ◽  
pp. 264-267
Author(s):  
Hong Ya Li ◽  
Tian Tian Zhang
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Dft Method ◽  
Detonation Pressure ◽  
Functional Theory ◽  
The Density Functional Theory ◽  
Equivalent Equation ◽  
Molecular Reactivity ◽  
Density Results

N-2’,4’-dinitrophenyl-3,3-dinitroazetidine (DNPDNAZ) is an important derivative of 3,3-dinitroazetidine (DNAZ). The density functional theory (DFT) method of the Amsterdam density functional (ADF) was used to calculate the geometry and frequencies. The detonation velocity (D) and detonation pressure (P) of DNPDNAZ were estimated using the nitrogen equivalent equation according to the experimental density. Results showed that the initial decomposition step of DNPDNAZ is the loss of NO2from C2 and N1 is the point of molecular reactivity,DandPare 7364.42 m·s-1and 23.75 GPa, respectively.

scholarly journals Structural characterization of light metal borohydrides by dispersion-corrected density functional theory modelling

2020 ◽  
Author(s):  
Mariana Derzsi ◽  
Agnieszka Starobrat ◽  
Tomasz Jaroń ◽  
Przemysław Malinowski ◽  
Wojciech Grochala
Keyword(s):  
Density Functional Theory ◽  
Structural Characterization ◽  
Density Functional ◽  
Light Metal ◽  
Functional Theory
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