Chemical Density Functional Theory Calculations Research Articles

Efficiency of Interstellar Nanodust Heating: Accurate Bottom-up Calculations of Nanosilicate Specific Heat Capacities.

Ultrasmall nanosized silicate grains are likely to be highly abundant in the interstellar medium. From sporadically absorbing energy from ultraviolet photons, these nanosilicates are subjected to significant instantaneous temperature fluctuations. These stochastically heated nanograins subsequently emit in the infrared. Previous estimates of the extent of the heating and emission have relied on empirical fits to bulk silicate heat capacities. The heat capacity of a system depends on the range of available vibrational modes, which for nanosized solids is dramatically affected by the constraints of finite size. Although experimental vibrational spectra of nanosilicates is not yet available, we directly take these finite size effects into account by using accurate vibrational spectra of low-energy nanosilicate structures from quantum chemical density functional theory calculations. Our results indicate that the heat capacities of ultrasmall nanosilicates are smaller than previously estimated, which would lead to a higher temperature and more intense infrared emission during stochastic heating. Specifically, we find that stochastically heated grains ultrasmall nanosilicates could be up to 35-80 K hotter than previously predicted. Our results could help to improve the understanding of infrared emission from ultrasmall nanosilicates in the ISM, which could be observed by the James Webb Space Telescope.

Deep purification of copper from Cu(II)-EDTA acidic wastewater by Fe(III) replacement/diethyldithiocarbamate precipitation

Cu(II)-EDTA is a highly stable typical metal-organic complex in a wide pH range (3.0–12.0) and it is difficult to deeply purify Cu(II) by conventional precipitation methods. In this study, Fe(III) replacement/diethyldithiocarbamate (DDTC) precipitation combined process is proposed as a promising strategy to achieve the deep purification of Cu(II) from Cu(II)-EDTA acidic wastewater. The underlying mechanism has also been systematically elucidated by chemical equilibriums, experiments, and density functional theory (DFT) calculations, laying a foundation for the development and application. Chemical equilibriums show that Fe(III) replacement favors the stoichiometric release of Cu(II) from Cu(II)-EDTA and the formation of Fe(III)-EDTA complex under acidic conditions. Experimentally, Cu(II) is removed (over 99.99%) and deeply purified (under 0.008 mg/L) under the optimal conditions, which is lower than the most stringent discharge standards of copper ions in electroplating effluent (<0.5 mg/L, China). DFT calculations reveal that DDTC could further precipitate the released free copper ions via the carbon disulfide (–C(=S)–S) chelating group while exhibiting a slight effect on the Fe(III) in Fe(III)-EDTA. Considering these results, the electronic structures of Cu(II) and Fe(III), as well as their interaction with EDTA and DDTC ligands, are discussed to understand the mechanism of Fe(III)/DDTC process. By introducing a low dosage of Fe(III), the DDTC could efficiently purify Cu(II) from the Cu(II)-EDTA acid wastewater and realize the near-zero discharge of metal pollutants in metal-organic complex wastewater. It is believed that the main findings may benefit the water pollution reduction and comprehensive recycling of metal resources.

Mechanistic Study of Silyl‐Assist Effect on 1,2‐cis‐α‐Glucosylation

AbstractThe stereoselectivity of the 1,2‐cis‐α‐glucosylation reaction has been reported to be enhanced by introducing a tert‐butyldimethylsilyl (TBS) protecting group into the glucosyl donor. Herein, the origin of this silyl‐assist effect was identified using chemical experiments and density functional theory (DFT) calculations. Glucosylation reactions using various glucosyl donors with different TBS group positions showed that α‐selectivity decreased when the TBS group position was further from the anomeric position. These systematic experiments showed that the silyl‐assist effect was mainly due to electronic factors. Comparing DFT calculations of oxocarbenium intermediates derived from typical glucosyl donors showed that the introduced TBS group contributed to enhanced electron density at the anomeric position. Chemical experiments and DFT calculations showed that introducing a TBS group near the anomeric position stabilized the cationic intermediate and promoted α‐selectivity.

Insights into the alloy-support synergistic effects for the CO2 hydrogenation towards methanol on oxide-supported Ni5Ga3 catalysts: An experimental and DFT study

Supported Ni-Ga alloys have emerged as potential catalyst to mitigate CO2 emissions by its conversion into methanol at mild conditions, however, its performance depends on the optimization of the alloy-support effects, which is unclear up to now. Herein, we investigate the influence of alloy-support synergy in the catalytic performance of Ni5Ga3 supported on SiO2, CeO2, and ZrO2, by combining in-depth structural, chemical and spectroscopic characterization and density functional theory (DFT) calculations. In situ DRIFTS confirmed further hydrogenation of key reaction intermediates in Ni5Ga3/ZrO2 surface, while weak CO2 adsorption in Ni5Ga3/SiO2 avoided intermediate stabilization on the surface and, strong interaction with Ni5Ga3/CeO2 poisoned interface active sites. Additionally, the relative energies of reactants and key intermediates in the three distinct regions of the catalyst (support surface, alloy surface, and alloy-support interface), calculated through DFT, allowed us to propose a reaction mechanism for the most promising catalyst, Ni5Ga3/ZrO2.

Novel High-Pressure Yttrium Carbide γ-Y_{4}C_{5} Containing [C_{2}] and Nonlinear [C_{3}] Units with Unusually Large Formal Charges.

Changes in the bonding of carbon under high pressure leads to unusual crystal chemistry and can dramatically alter the properties of transition metal carbides. In this work, the new orthorhombic polymorph of yttrium carbide, γ-Y_{4}C_{5}, was synthesized from yttrium and paraffin oil in a laser-heated diamond anvil cell at ∼50 GPa. The structure of γ-Y_{4}C_{5} was solved and refined using insitu synchrotron single-crystal x-ray diffraction. It includes two carbon groups: [C_{2}] dimers and nonlinear [C_{3}] trimers. Crystal chemical analysis and density functional theory calculations revealed unusually high noninteger charges ([C_{2}]^{5.2-} and [C_{3}]^{6.8-}) and unique bond orders (<1.5). Our results extend the list of possible carbon states at extreme conditions.

Distance Effects of Phenylpiperazine-Containing Methacrylic Polymers on Optical and Structural Properties.

New materials based on methacrylic polymers modified with 1-(4-nitrophenyl)piperazine side chains, differing in the distance of the chromophore from the polymer main chain and/or the separation between the chromophoric units in the chain, are obtained and characterized in terms of their potential applications in optoelectronic devices. The surface, structural, and optical properties of the investigated materials are determined using atomic force microscopy, spectroscopic ellipsometry combined with transmission measurements, Raman and Fourier transform infrared spectroscopy, as well as cyclic voltammetry. The relevant model systems are additionally analyzed with quantum chemical density functional theory calculations in order to enable the generalization of the structure–photophysical property relationships for the optimization of the material features. It is found that the structural modification of the material, relying on the transit of the piperazine moiety away from the main polymer chain, leads to the hypsochromic shift of the absorption spectrum. Moreover, the lowest refractive index values are obtained for the polymer with a distant ethylene group in the side-chains and increased separation between the piperazine units. It was shown that the optical energy band gaps of the investigated piperazine-containing polymers are in the range from 2.73 to 2.81 eV, which reveals their promising potential for the advances in photovoltaics, field effect transistors, or electrochromic devices as an alternative for other widely applied polymer materials.

A Catalyst-Controlled Enantiodivergent Bromolactonization.

A catalyst-controlled enantiodivergent bromolactonization of olefinic acids has been developed. Quinine-derived amino-amides bearing the same chiral core but different achiral aryl substituents were used as the catalysts. Switching the methoxy substituent in the aryl amide system from meta- to ortho-position results in a complete switch in asymmetric induction to afford the desired lactone in good enantioselectivity and yield. Mechanistic studies, including chemical experiments and density functional theory calculations, reveal that the differences in steric and electronic effects of the catalyst substituent alter the reaction mechanism.

Porous Fluorocarbon from Rice Husk for the Efficient Separation of Gases.

A porous fluorocarbon sorbent is synthesized from rice husk (RH) in a microwave reactor and then evaluated for the adsorption of different gases (CH4, CO2, and N2). The fluorocarbon is characterized by Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD), Brunauer–Emmett–Teller (BET), Raman spectroscopy, Thermal gravimetric analysis (TGA), and X‐ray photoelectron spectroscopy (XPS). Significant enhancement in the surface area of activated carbon material is obtained from 29 to 531 m2 g−1 after removing naturally present silica in RH. Results reveal that rice husk fluorocarbon (RHF) has a higher adsorption affinity for CO2 (1.8 mmol g−1) than that of the sulfonated rice husk (RHS) (1.4 mmol g−1) at 298 K while the corresponding separation factor of CO2/CH4 is 4 and 3; respectively. Higher separation factors of 12 and 10 are observed for the binary system of CO2/N2, respectively. Quantum chemical density functional theory (DFT) calculations agree with the experimental observations. They reveal that RHF exhibits strong columbic interactions with considerable interaction energies of −87.85, −76.75, and −55.65 kcal mol−1 with CO2, CH4, and N2 gases; respectively. Finally, the adsorption process results are highly reproducible, with a small decrease in the adsorption capacity of less than 5% after repeated trials.

Formation of Interstellar Silicate Dust via Nanocluster Aggregation: Insights From Quantum Chemistry Simulations

The issue of formation of dust grains in the interstellar medium is still a matter of debate. One of the most developed proposals suggests that atomic and heteromolecular seeds bind together to initiate a nucleation process leading to the formation of nanostructures resembling very small grain components. In the case of silicates, nucleated systems can result in molecular nanoclusters with diameters ≤ 2 nm. A reasonable path to further increase the size of these proto-silicate nanoclusters is by mutual aggregation. The present work deals with modeling this proto-silicate nanocluster aggregation process by means of quantum chemical density functional theory calculations. We simulate nanocluster aggregation by progressively reducing the size of a periodic array of initially well-separated nanoclusters. The resulting aggregation leads to a set of silicate bulk structures with gradually increasing density which we analyze with respect to structure, energetics and spectroscopic properties. Our results indicate that aggregation is a highly energetically favorable process, in which the infrared spectra of the finally formed amorphous silicates match well with astronomical observations.

Probing the Local Atomic Structure of In and Cu in Sphalerite by XAS Spectroscopy Enhanced by Reverse Monte Carlo Algorithm

The distortion of atomic structure around In and Cu dopants in sphalerite ZnS was explored by extended X-ray absorption fine structure (EXAFS) spectroscopy enhanced by reverse Monte Carlo (RMC) simulation (RMC-EXAFS method). These data were complemented with quantum chemical Density Functional Theory (DFT) calculations and theoretical modeling of X-ray absorption near edge spectroscopy (XANES) spectra. The RMC-EXAFS method showed that in the absence of Cu, the In-bearing solid solution is formed via the charge compensation scheme 3Zn2+↔2In3+ + □, where □ is a Zn vacancy. The coordination spheres of In remain undistorted. Formation of the solid solution in the case of (In, Cu)-bearing sphalerites follows the charge compensation scheme 2Zn2+↔Cu+ + In3+. In the solid solution, splitting of the interatomic distances in the 2nd and 3rd coordination spheres of In and Cu is observed. The dopants’ local atomic structure is slightly distorted around In but highly distorted around Cu. The DFT calculations showed that the geometries with close arrangement (clustering) of the impurities—In and Cu atoms, or the In atom and a vacancy—are energetically more favorable than the random distribution of the defects. However, as no heavy In atoms were detected in the 2nd shell of Cu by means of EXAFS, and the 2nd shell of In was only slightly distorted, we conclude that the defects are distributed randomly (or at least, not close to each other). The disagreement of the RMC-EXAFS fittings with the results of the DFT calculations, according to which the closest arrangement of dopants is the most stable configuration, can be explained by the presence of other defects of the sphalerite crystal lattice, which were not considered in the DFT calculations.

Vibrational Dynamics of a Chiral Smectic Liquid Crystal Undergoing Vitrification and Cold Crystallization

Vibrational dynamics in the glass transition and the cold crystallization process of (S)-4′-(1-methyloctyloxycarbonyl) biphenyl-4-yl 4-[7-(2,2,3,3,4,4,4-heptafluorobutoxy) heptyl-1-oxy]-benzoate (3F7HPhH7) was studied by Fourier transform infrared spectroscopy (FTIR) during cooling/heating experimental runs. The measured spectra processing was supported by quantum chemical density functional theory (DFT) calculations (frequency assignments). The perturbation-correlation moving window two-dimensional analysis (PCMW2D) was performed to examine how the height of individual absorption bands change under with temperature. Two-dimensional correlation analysis (2D-COS) was used to detect freezing-in or activation of the stochastic movements during the vitrification and the cold crystallization processes. Upon cooling, the vitrification process involves freezing-in of the stochastic movements of ester groups. Upon heating, as the cold crystallization process begins, the first to respond are the vibrations of the C–O–C and C=O groups in the rigid core.

Producing elemental sulfur from SO2 by calcium loaded activated coke: Enhanced activity and selectivity

SO2 carbothermal reduction is one of the promising strategies to convert SO2 to elemental sulfur, while the long-term challenge is to simultaneously improve the reactivity and selectivity. In this work, we demonstrate an effective approach for enhancing both the activity and selectivity of activated coke (AC) for SO2 carbothermal reduction by controllably loading catalytic Ca species. Ca-loaded ACs were prepared via a simple ultrasound assisted liquid phase impregnation method, in which the pore structure as well as CaCl2 distribution in Ca-loaded ACs can be optimized by tuning CaCl2 loading content. Dynamic experiments show that CaCl2-loaded ACs exhibit much higher SO2 removal rates as compared with pure AC, indicating the promoting role of Ca loading in SO2 carbothermal reduction activity. Such enhanced activity of CaCl2-loaded ACs is attributed to the decrease of activation energy according to the kinetic parameters calculated from Random Pore Model (RPM). By calculating and correlating the amounts of consumed reactants and reaction products, AC loaded with 30- wt% CaCl2 can achieve a record-high elemental sulfur production selectivity of 80%, which should be contributed by both the reactions of SO2 + C → CO2 + S and 2CO + SO2 → 2CO2 + S. Chemical environment investigations and density functional theory (DFT) calculations further demonstrate that the C-O-Ca structure in Ca-loaded AC can weaken the C-O bond in reaction intermediates and thereby reduce the energy needed for O transfer, making SO2 reduction feasible to occur. In addition, we also evaluate the recyclability of catalyst CaCl2 that is proven to be easily recovered and recirculated. This work provides a facile strategy to improve the reactivity and selectivity for SO2 carbothermal reduction, holding great application potentials in flue gas desulfurization.

Chiral Derivatives of 2-Aminotribenzotriquinacene: Synthesis and Optical Resolution.

Starting from a hitherto unknown 2-aminotribenzotriquinacene, several 2-amino-3-X-substituted TBTQ derivatives, all bearing a single ortho-difunctionalized indane wing, were synthesized as rigid and chiral building blocks for the potential construction of complex supramolecular architectures. Efficient access to two pairs of enantiomeric TBTQ derivatives, namely, the peripheral ortho-nitroaniline (X = NO2) and the related anthranilic acid (X = CO2H), was developed using chiral auxiliaries as the resolving reagents. The structure of the intermediate diastereomers was confirmed by 1H and 13C NMR spectroscopy, high-resolution mass spectroscopy (HRMS), and polarimetry. The absolute configuration of the optically active derivatives was confirmed by quantum chemical time-dependent density functional theory (TD-DFT) calculations of the theoretical electronic circular dichroism (ECD) spectra and by single-crystal X-ray structure analysis of a synthesis intermediate.

Synthesis of a new class of corrosion inhibitors derived from natural fatty acid: 13‐Docosenoic acid amide derivatives for oil and gas industry

As corrosion inhibitors, a series of new amide derivatives of 13‐docosenoic acid was synthesized in yields of above 90% by reacting 13-docosenoic acid with primary and secondary aliphatic and aromatic amines. The inhibition efficiencies (%IEs) of these compounds at various concentrations for the suppression of corrosion of mild steel in 1.00 M HCl exposed for 96 h (4 days) at temperatures in the range 298–333 K were measured via gravimetric corrosion measurements. At 100 ppm, all compounds yielded satisfactory corrosion %IE in 1.00 M HCl; compounds 2 and 7 exhibited remarkable %IE of 70.0 and 74.7%, respectively. The results of gravimetric measurements further revealed that compound 7 performed excellently at 60 °C, with %IE = 96.8 at 500 ppm. Quantum chemical density functional theory (DFT) calculations helped predict that compound 7 should have more aromatic character, enabling it to serve as a donor-center for the empty d-orbital of the metal atoms, leading to higher corrosion IE. The adsorption of the inhibitor molecules on the surface of mild steel followed the Langmuir adsorption model, and the free energy of adsorption (ΔGads) value indicated that the inhibitors are adsorbed through a combined physisorption and chemisorption mechanism to provide effective surface coverage.

Recognition of the Enzymatically Active and Inhibitive Oxygenous Groups on WO3-x Quantum Dots by Chemical Deactivation and Density Functional Theory Calculations.

The design and construction of efficient nanozymes are vital for bio/chemo-sensing applications, while the systematic catalytic mechanism study is the prerequisite. Tungsten oxide (WO3-x) quantum dots (QDs), an alternative to conventional heavy metal-containing semiconductor QDs, possess peroxidase-like activity but limited catalytic efficiency. Therefore, the functions of the typical oxygenous groups in determining the enzymatic activity of the WO3-x QDs by target-specifically shielding the carboxyl (-COOH), hydroxyl (-OH), or carbonyl (-C═O) groups, respectively, using a chemical titration method. The results show that the -C═O groups could accelerate the nanozymatic catalysis kinetically, while the -OH ones were the catalytically inhibitive sites, which were further corroborated by the density functional theory (DFT) computations. The application potential of the WO3-x derivatives with an enhanced catalytic ability was verified via the colorimetric cholesterol sensing. The proposed method based on the benzoic anhydride (BA)-modified WO3-x QDs with deactivated -OH groups showed a wider linear range and higher sensitivity than those based on the unmodified ones.

Theoretical studies of infrared signatures of proton-bound amino acid dimers with homochiral and heterochiral moieties.

Proton-bound homochiral and heterochiral dimers, X-H+ -X, of five amino acids (X = Ser, Ala, Thr, Phe, and Arg) are investigated theoretically using quantum chemical density functional theory (DFT) calculations and molecular dynamics simulations with the aim to unveil diastereomer-specific mid-infrared (mid-IR) absorption bands in the spectral range of 1000 to 1800 cm-1 . The theoretical calculations performed in this work imply that all systems, except Ala2 H+ , have distinct mid-IR absorption bands in homochiral and heterochiral configurations, which make them appropriate systems to be studied experimentally with mid-IR spectroscopy. We show that intermolecular interaction with the side chain, in the form of hydrogen bonding or cation-π interaction, is necessary for chiral effects to be present in the mid-IR spectra of proton-bound dimers of amino acids. We also report new conformers for Ala2 H+ , Thr2 H+ , Phe2 H+ , and Arg2 H+ , which were not found in earlier studies of these dimers.

Linear, second and third order nonlinear optical properties of novel noncentrosymmetric donor-acceptor configure chalcone derivatives: A dual approach study

Herein we report the crystal structure geometry, optoelectronic and charge transport properties of (E)-1-(4-Bromophenyl)-3-(2-chlorophenyl)prop-2-en-1-one (1), (E)-3-(3-Bromophenyl)-1-(4-methoxyphenyl)prop-2-en-1-one (2) and (E)-3-(4-Chlorophenyl)-1-(2-furyl)prop-2-en-1-one (3) chalcone derivatives. In experimental part UV–vis-NIR, X-ray diffraction and Photoluminescence spectroscopy techniques were used. Additionally, quantum chemical density functional theory calculations were executed with a clear view to explore the linear optical, second and third-order nonlinear optical (NLO) properties as well as transfer integrals of all three systems. The experimental and theoretically calculated properties are found to be in excellent accord with each other. Comprehensible intra- and inter-molecular charge transport was observed from occupied to unoccupied molecular orbitals illuminating that these chalcones would be good choice to be used in various semiconductor devices. The compound (3) is found to have better NLO activities and thermal stability compared to (1) and (2). Larger electron transfer integral values than hole ones exposed that studied compounds would be better electron transport materials and can function as n-type in organic semiconductor devices.

Synthesis and characterization of new N-{4,6-bis[2-(het)arylvinyl]pyrimidin-2-yl}-substituted polycyclic aromatic imides

Two series of new N-{4,6-bis[2-(het)arylvinyl]pyrimidin-2-yl}-substituted aromatic polycyclic imides were synthesized. The synthesized chromophores were characterized by UV and fluorescence spectroscopy, cyclic voltammetry, and quantum chemical density functional theory calculations. A change in the nature of aryl (hetaryl) moieties was found to cause changes in the optical properties of both solutions of these compounds and thin films prepared from these compounds. The replacement of the phthalimide moiety by the 1,8-naphthalimide one has led to a significant increase in the lowest unoccupied molecular orbital energy.

Lithium–functionalization of Pyrrole–n–carboxylic Acids (n=1, 2, 3)

Functionalization processes of neutral and ionic forms of the singular lithium element (Li/Li+) by the pyrrole–n–carboxylic acid (PnCA; n=1, 2, 3) have been investigated based on the quantum chemical density functional theory (DFT) calculations. To this aim, molecular and atomic scales parameters have been obtained for the optimized structures of original and Li/Li+ functionalized complex models of PnCA. The results have indicated that the structural shapes and the O8 dominant atom properties are similar to P1CA and P3CA models but different from P2CA model. Moreover, the adsorption energies have indicated that the P3CA model could be considered as the best choice for both of Li and Li+ functionalization processes. The orbital distribution patterns and dipole moments have also approved the Li/Li+ functionalization by the PnCA species. As a result, the PnCA species could be suggested as suitable adsorbents of neutral and ionic forms of the Li element.

Microhydration Structures of Protonated Oxazole

The initial microhydration structures of the protonated pharmaceutical building block oxazole (Ox), H+Ox-Wn≤4, are determined by infrared photodissociation (IRPD) spectroscopy combined with quantum chemical dispersion-corrected density functional theory calculations (B3LYP-D3/aug-cc-pVTZ). Protonation of Ox, achieved by chemical ionization in a H2-containing plasma, occurs at the most basic N atom. The analysis of systematic shifts of the NH and OH stretch vibrations as a function of the cluster size provides a clear picture for the preferred cluster growth in H+Ox-Wn. For n = 1-3, the IRPD spectra are dominated by a single isomer, and microhydration of H+Ox with hydrophilic protic W ligands occurs by attachment of a hydrogen-bonded (H-bonded) Wn solvent cluster to the acidic NH group via an NH···O H-bond. Such H-bonded networks are stabilized by strong cooperativity effects. This is in contrast to previously studied hydrophobic ligands, which prefer interior ion solvation. The strength of the NH···O ionic H-bond increases with the degree of hydration because of the increasing proton affinity (PA) of the Wn cluster. At n = 4, proton-transferred structures of the type Ox-H+Wn become energetically competitive with H+Ox-Wn structures, because differences in solvation energies can compensate for the differences in the PAs, and barrierless proton transfer from H+Ox to the Wn solvent subcluster becomes feasible. Indeed, the IRPD spectrum of the n = 4 cluster is more complex suggesting the presence of more than one isomer, although it lacks unequivocal evidence for the predicted intracluster proton transfer.